Patent Document

FIELD OF THE INVENTION AND RELATED ART 
   The present invention relates to an organic luminescence device (also called an organic electroluminescence device or organic EL device) for use in a planar light source, a planar display, etc. Particularly, the present invention relates to a novel metal coordination compound and a luminescence device having a high luminescence efficiency and causing little change with time by using a metal coordination compound represented by formula (1) appearing hereinafter. 
   An old example of organic luminescence device is, e.g., one using luminescence of a vacuum-deposited anthracene film (Thin Solid Films, 94 (1982) 171). In recent years, however, in view of advantages, such as easiness of providing a large-area device compared with an inorganic luminescence device, and possibility of realizing desired luminescence colors by development of various new materials and drivability at low voltages, an extensive study thereon for device formation as a luminescence device of a high-speed responsiveness and a high efficiency, has been conducted. 
   As precisely described in Macromol. Symp. 125, 1-48 (1997), for example, an organic EL device generally has an organization comprising a pair of upper and lower electrodes formed on a transparent substrate, and organic material layers including a luminescence layer disposed between the electrodes. 
   In the luminescence layer, aluminum quinolinol complexes (inclusive of Alq3 shown hereinafter as a representative example) having an electron-transporting characteristic and a luminescence characteristic, are used for example. In a hole-transporting layer, a material having an electron-donative property, such as a triphenyldiamine derivative (inclusive of α-NPD shown hereinafter as a representative example), is used for example. 
   Such a device shows a current-rectifying characteristic such that when an electric field is applied between the electrodes, holes are injected from the anode and electrons are injected from the cathode. 
   The injected holes and electrons are recombined in the luminescence layer to form excitons, which emit luminescence when they are transitioned to the ground state. 
   In this process, the excited states include a singlet state and a triplet state and a transition from the former to the ground state is called fluorescence and a transition from the latter is called phosphorescence. Materials in theses states are called singlet excitons and triplet excitons, respectively. 
   In most of the organic luminescence devices studied heretofore, fluorescence caused by the transition of a singlet exciton to the ground state, has been utilized. On the other hand, in recent years, devices utilizing phosphorescence via triplet excitons have been studied. 
   Representative published literature may include: 
   Article 1: Improved energy transfer in electrophosphorescent device (D. F. O&#39;Brien, et al., Applied Physics Letters, Vol. 74, No. 3, p. 422 (1999)); and 
   Article 2: Very high-efficiency green organic light-emitting devices based on electrophosphorescence (M. A. Baldo, et al., Applied Physics Letters, Vol. 75, No. 1, p. 4 (1999)). 
   In these articles, a structure including four organic layers sandwiched between the electrodes, and the materials used therein include carrier-transporting materials and phosphorescent materials, of which the names and structures are shown below together with their abbreviations.
         Alq3: aluminum quinolinol complex   α-NPD: N4,N4′-di-naphthalene-1-yl-N4,N4′-diphenyl-biphenyl-4, 4′-diamine   CBP: 4,4′-N,N′-dicarbazole-biphenyl   BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline   PtOEP: platinum-octaethylporphyrin complex   Ir(ppy) 3 : iridium-phenylpyridine complex 
                         
 
 
       

   The above-mentioned Articles 1 and 2 both have reported structures, as exhibiting a high efficiency, including a hole-transporting layer comprising α-NPD, an electron-transporting layer comprising Alq3, an exciton diffusion-preventing layer comprising BCP, and a luminescence layer comprising CBP as a host and ca. 6% of PtOEP or Ir(ppy) 3  as a phosphorescent material dispersed in mixture therein. 
   Such a phosphorescent material is particularly noted at present because it is expected to provide a high luminescence efficiency in principle for the following reasons. More specifically, excitons formed by carrier recombination comprise singlet excitons and triplet excitons in a probability ratio of 1:3. Conventional organic EL devices have utilized fluorescence of which the luminescence efficiency is limited to at most 25%. On the other hand, if phosphorescence generated from triplet excitons is utilized, an efficiency of at least three times is expected, and even an efficiency of 100%, i.e., four times, can be expected in principle, if a transition owing to intersystem crossing from a singlet state having a higher energy to a triplet state is taken into account. 
   However, like a fluorescent-type device, such an organic luminescence device utilizing phosphorescence is generally required to be further improved regarding the deterioration of luminescence efficiency and device stability. 
   The reason of the deterioration has not been fully clarified, but the present inventors consider as follows based on the mechanism of phosphorescence. 
   In the case where the luminescence layer comprises a host material having a carrier-transporting function and a phosphorescent guest material, a process of phosphorescence via triplet excitons may include unit processes as follows:
         1. transportation of electrons and holes within a luminescence layer,   2. formation of host excitons,   3. excitation energy transfer between host molecules,   4. excitation energy transfer from the host to the guest,   5. formation of guest triplet excitons, and   6. transition of the guest triplet excitons to the ground state and phosphorescence.       

   Desirable energy transfer in each unit process and luminescence are caused in competition with various energy deactivation processes. 
   Needless to say, a luminescence efficiency of an organic luminescence device is increased by increasing the luminescence quantum yield of a luminescence center material. 
   Particularly, in a phosphorescent material, this may be attributable to a life of the triplet excitons which is longer by three or more digits than the life of a singlet exciton. More specifically, because it is held in a high-energy excited state for a longer period, it is liable to react with surrounding materials and cause polymer formation among the excitons, thus incurring a higher probability of deactivation process resulting in a material change or life deterioration. 
   A luminescence device is desired to exhibit high efficiency luminescence and show a high stability. Particularly, it is strongly desired to provide a luminescence material compound which is less liable to cause energy deactivation in a long life of excited energy state and is also chemically stable, thus providing a longer device life. 
   SUMMARY OF THE INVENTION 
   Accordingly, principal objects of the present invention are to provide a luminescence material which exhibits a high luminescence efficiency and retains a high luminance for a long period, and also provide a luminescence device and a display apparatus using the same. 
   In the present invention, a metal complex is used as a luminescence material, particularly a novel luminescent metal complex compound comprising iridium as a center metal and an aromatic group of formula (5) appearing hereinafter as a part of a ligand or as a substituent of a ligand. 
   More specifically, the present invention provides as a luminescence material a metal coordination compound represented by formula (1) below:
 
ML m L′ n   (1), 
 
wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3 and n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial structure MLm is represented by formula (2) shown below and a partial structure ML′ n  is represented by formula (3) or (4) shown below: 
                        
 
 
 
wherein CyN1 and CyN2 are each cyclic group capable of having a substituent, including a nitrogen atom and bonded to the metal atom M via the nitrogen atom; CyC1 and CyC2 are each cyclic group capable of having a substituent, including a carbon atom and bonded to the metal atom M via the carbon atom with the proviso that the cyclic group CyN1 and the cyclic group CyC1 are bonded to each other via a covalent bond and the cyclic group CyN2 and the cyclic group CyC2 are bonded to each other via a covalent bond;
         the optional substituent of the cyclic groups is selected from a halogen atom, cyano group, a nitro group, a trialkylsilyl group of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom, or an aromatic group capable of having a substituent (that is a halogen atom, a cyano atom, a nitro atom, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C—C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom);   E and G are independently a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom, or an aromatic group capable of having a substituent (that is a halogen atom, a cyano atom, a nitro atom, a trialkylsilyl group of which the alkyl groups are independently a linear or branched alkyl group having 1-8 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom; and   at least one of the optional substituent(s) of the cyclic groups, and the cyclic groups CyC1 and CyC2 include an aromatic group capable of having a substituent represented by the following formula (5): 
                         
 
 
 
wherein the aromatic group of the formula (5) is bonded to CyN1, CyN2, CyC1 or CyC2 via a single bond when the aromatic group is the optional substituent(s) of the cyclic groups, and the aromatic group of the formula (5) is bonded to CyN1 or CyN2 via a single bond and bonded to the metal atom M via a single bond when the aromatic group is CyC1 or CyC2;
   Y denotes C═O, CRR′, C═C(CN) 2 , O or S wherein R and R′ are independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—or —C≡C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom, or an aromatic group capable of having a substituent (that is a halogen atom, a cyano atom, a nitro atom, a trialkylsilyl group of which the alkyl groups are independently a linear or branched alkyl group having 1-8 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C═C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom); and   the optional substituent of the aromatic group of the formula (5) is selected from a halogen atom, cyano group, a nitro group, a trialkylsilyl group of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom, or an aromatic group capable of having a substituent (that is a halogen atom, a cyano atom, a nitro atom, a linear or branched alkyl group having 1 to 20 carbon atoms of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom) with the proviso that an adjacent pair of substituents can be bonded to form a cyclic structure.       

   Preferred embodiments of the metal coordination compound of the formula (1) according to the present invention include the following: 
   A metal coordination compound having a partial structure ML′ n  represented by the formula (3) in the formula (1). 
   A metal coordination compound having a partial structure ML′ n  represented by the formula (4) in the formula (1). 
   A metal coordination compound, wherein n is 0 in the formula (1). 
   A metal coordination compound, wherein the group Y in the formula (5) is C═O or CRR′. 
   A metal coordination compound wherein the cyclic groups CyC1 in the formula (1) and CYC2 in the formula (3) are independently selected from phenyl group, thienyl group, thianaphthyl group, naphthyl group, pyrenyl group, 9-fluorenonyl group, fluorenyl group, dibenzofuryl group, dibenzothienyl group, or carbazolyl group, as an aromatic cyclic group capable of having a substituent with the proviso that the aromatic cyclic group can include one or two CH groups that can be replaced with a nitrogen atom, particularly selected from phenyl group or 2-fluorenyl group. 
   A metal coordination compound, wherein the cyclic groups CyN1 in the formula (2) and CyN2 in the formula (3) are independently selected from pyridyl group, pyridazinyl group, and pyrimidinyl group, particularly pyridyl group, as an aromatic cyclic group capable of having a substituent. 
   A metal coordination compound, wherein the cyclic groups CyN1, CyN2, CyC1 and CyC2 are independently non-substituted, or have a substituent selected from a halogen atom and a linear or branched alkyl group having 1 to 20 carbon atoms {of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—, or a divalent aromatic group capable of having a substituent (that is a halogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom)), and the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom}. 
   A metal coordination compound, wherein M in the formula (1) is iridium. 
   A metal coordination compound represented by the following formula (6): 
                        
 
 
 
wherein X denotes CRR′, O or S where R and R′ are independently a linear or branched alkyl group of formula: C n H 2n+1 — in which n is an integer of 1-20, the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—and also can include a hydrogen atom that can be optionally replaced with a fluorine atom;
         R2 denotes a hydrogen atom; a fluorine atom; a linear or branched alkyl group of formula: C n H 2n+1 — in which n is an integer of 1-20, the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O— and also can include a hydrogen atom that can be optionally replaced with a fluorine atom; a phenyl group capable of having a substituent; a 9,9-dialkylfluorenyl group (of which the alkyl groups are independently a linear or branched alkyl group of formula: C n H 2n+1 — in which n is an integer of 1-20, the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—and also can include a hydrogen atom that can be optionally replaced with a fluorine atom); a dibenzofuranyl group capable of having a substituent; and a dibenzothienyl group capable of having a substituent; the optional substituent of phenyl group, 9,9-dialkylfluorenyl group, dibenzofuranyl group and dibenzothienyl group is a fluorine atom or a linear or branched alkyl group of formula: C n H 2n+1 — in which n is an integer of 1-20, the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O— and also can include a hydrogen atom that can be optionally replaced with a fluorine atom.       

   The present invention also provides an electroluminescence device, comprising: a pair of electrodes disposed on a substrate, and a luminescence unit comprising at least one organic compound disposed between the electrodes, wherein the organic compound comprises a metal coordination compound represented by the formula (1) described above. 
   In the luminescence device, a voltage is applied between the electrodes to emit light. 
   In a preferred embodiment of the electroluminescence device, a voltage is applied between the electrodes to emit phosphorescence. 
   The present invention further provides a picture display apparatus, comprising an electroluminescence device described above and a means for supplying electric signals to the electroluminescence device. 
   These and other objects, features and advantages of the present invention will become more apparent upon a consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings. 

   
     BRIEF DESCRIPTION OF THE DRAWINGS 
       FIGS. 1A ,  1 B and  1 C illustrate embodiments of the luminescence device according to the present invention, respectively. 
       FIG. 2  schematically illustrates a panel structure including an EL device and drive means. 
   

   DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
   Basic structures of organic luminescence (EL) devices formed according to the present invention are illustrated in  FIGS. 1A ,  1 B and  1 C. 
   As shown in these figures, an organic luminescence device generally comprises, on a transparent substrate  15 , a 50 to 200 nm-thick transparent electrode  14 , a plurality of organic film layers and a metal electrode  11  formed so as to cover the organic layers. 
     FIG. 1A  shows an embodiment wherein the organic luminescence device comprises a luminescence layer  12  and a hole-transporting layer  13 . The transparent electrode  14  may comprise ITO, etc., having a large work function so as to facilitate hole injection from the transparent electrode  14  to the hole-transporting layer  13 . The metal electrode  11  comprises a metal material having a small work function, such as aluminum, magnesium or alloys of these elements, so as to facilitate electron injection into the organic luminescence device. 
   The luminescence layer  12  comprises a compound (metal coordination compound) according to the present invention. The hole-transporting layer  13  may comprise, e.g., a triphenyldiamine derivative, as represented by α-NPD mentioned above, and also a material having an electron-donative property as desired. 
   A device organized above exhibits a current-rectifying characteristic, and when an electric field is applied between the metal electrode  11  as a cathode and the transparent electrode  14  as an anode, electrons are injected from the metal electrode  11  into the luminescence layer  12 , and holes are injected from the transparent electrode  15 . The injected holes and electrons are recombined in the luminescence layer  12  to form excitons having high energy potential, which cause luminescence during transition to the ground state. In this instance, the hole-transporting layer  13  functions as an electron-blocking layer to increase the recombination efficiency at the boundary between the luminescence layer layer  12  and the hole-transporting layer  13 , thereby providing an enhanced luminescence efficiency. 
   Further, in the structure of  FIG. 1B , an electron-transporting layer  16  is disposed between the metal electrode  11  and the luminescence layer  12  in FIG.  1 A. As a result, the luminescence function is separated from the functions of electron transportation and hole transportation to provide a structure exhibiting more effective carrier blocking, thus increasing the luminescence efficiency. The electron-transporting layer  16 , may comprise, e.g., an oxadiazole derivative. 
     FIG. 1C  shows another desirable form of a four-layer structure, including a hole-transporting layer  13 , a luminescence layer  12 , an exciton diffusion prevention layer  17  and an electron-transporting layer  16 , successively from the side of the transparent electrode  14  as the anode. 
   The luminescence materials used in the present invention are most suitably metal coordination compounds represented by the above-mentioned formulae (1) to (5), which are found to cause high-efficiency luminescence, retain high luminance for a long period and show little deterioration by current passage. 
   The metal coordination compound of the present invention emits phosphorescence, and its lowest excited state is believed to be an MLCT* (metal-to-ligand charge transfer) excited state or π-π* excited state in a triplet state, and phosphorescence is caused at the time of transition from such a state to the ground state. 
   Hereinbelow, methods for measurement of some properties and physical values described herein for characterizing the luminescence material of the present invention will be described. 
   (1) Judgment between phosphorescence and fluorescence 
   The identification of phosphorescence was effected depending on whether deactivation with oxygen was caused or not. A solution of a sample compound in chloroform after aeration with oxygen or with nitrogen is subjected to photoillumination to cause photo-luminescence. The luminescence is judged to be phosphorescence if almost no luminescence attributable to the compound is observed with respect to the solution aerated with oxygen but photo-luminescence is confirmed with respect to the solution aerated with nitrogen. The phosphorescence of all the compounds of the present invention has been confirmed by this method unless otherwise noted specifically. 
   (2) Phosphorescence yield (a relative quantum yield, i.e., a ratio of an objective sample&#39;s quantum yield Φ (sample) to a standard sample&#39;s quantum yield Φ (st)) is determined according to the following formula:
 
Φ(sample)/Φ(st)=[Sem(sample)/Iabs(sample)]/[Sem(st)/Iabs(st)], 
 
wherein Iabs(st) denotes an absorption coefficient at an excitation wavelength of the standard sample; Sem(st), a luminescence spectral a real intensity when excited at the same wavelength; Iabs(sample), an absorption coefficient at an excitation wavelength of an objective compound; and Sem(sample), a luminescence spectral areal intensity when excited at the same wavelength.
 
   Phosphorescence yield values described herein are relative values with respect to a phosphorescence yield Φ=1 of Ir(ppy) 3  as a standard sample. 
   (3) A method of measurement of phosphorescence life is as follows. 
   A sample compound is dissolved in chloroform and spin-coated onto a quartz substrate in a thickness of ca. 0.1 μm and is exposed to pulsative nitrogen laser light at an excitation wavelength of 337 nm at room temperature by using a luminescence life meter (made by Hamamatsu Photonics K.K.). After completion of the excitation pulses, the decay characteristic of luminescence intensity is measured. 
   When an initial luminescence intensity is denoted by I 0 , a luminescence intensity after t(sec) is expressed according to the following formula with reference to a luminescence life τ(sec):
 
 I=I   0 ·exp(− t /τ). 
 
   The luminescence material (metal coordination compound) of the present invention exhibited high phosphorescence quantum yields of 0.11 to 0.9 and short phosphorescence lives of 0.1 to 40 μsec. A short phosphorescence life becomes a condition for causing little energy deactivation and exhibiting an enhanced luminescence efficiency. More specifically if the phosphorescence life is long, the number of triplet state molecules maintained for luminescence is increased, and the deactivation process is liable to occur, thus resulting in a lower luminescence efficiency particularly at the time of a high-current density. The material of the present invention has a relatively short phosphorescence life thus exhibiting a high phosphorescence quantum yield, and is therefore suitable as a luminescence material for an EL device. 
   As a result of various studies of ours, it has been found that an organic EL device using the metal coordination compound of the formula (1) as a principal luminescence material causes high-efficiency luminescence, retains high luminance for a long period and shows little deterioration by current passage. 
   In the formula (1) representing the metal coordination compound of the present invention, n may preferably 0 or 1, more preferably 0. Further, the partial structure ML′n may preferably comprise the aromatic group represented by the above-mentioned formula (5). In the formula (5), Y may preferably comprise C═O or CRR′. When Y is CRR′ where R and R′ are CH 3 , the metal coordination compound of the formula (I) may preferably have no substituent. Particularly, when CyC1 is FL2 (appearing hereinafter) where R and R′ are CH 3  and CyN1 is Pi, R1 to R4 (as substituents for Pi and FL2) may preferably be hydrogen atom at the same time. 
   In the present invention, by incorporating the aromatic group of the formula (5) into the metal coordination compound of the formula (1), it becomes possible to control an emission wavelength (particularly to provide a long emission wavelength). The presence of the aromatic group of the formula (5) is effective in enhancing a solubility of the metal coordination compound of the present invention in an organic solvent, thus facilitating a purification thereof by recrystallization or column chromatography. As a result, the metal coordination compound of the present invention is suitable as a luminescence material for the organic EL device. 
   Further, as shown in Examples appearing hereinafter, it has been substantiated that the metal coordination compound of the present invention exhibited an excellent stability in a continuous current passage test. This may be attributable to incorporation of the aromatic group of the formula (5) into the molecular structure of the metal coordination compound of the formula (1) according to the present invention. More specifically, a change in intermolecular interaction due to the introduction of the aromatic group of the formula (5) allows an intermolecular interaction of the metal coordination compound with, e.g., a host material to suppress formation of exciton associates causing thermal deactivation, thus reducing a quenching process thereby to improve phosphorescence yield and device characteristics. 
   The luminescence device according to the present invention may preferably be an electroluminescence device of the type wherein a layer of the metal coordination compound of the formula (1) is disposed between opposing two electrodes and a voltage is applied between the electrodes to cause luminescence, as shown in  FIGS. 1A ,  1 B and  1 C. 
   For the application to a display, a drive system using a thin-film transistor (TFT) drive circuit according to an active matrix-scheme may be used. Hereinbelow, an embodiment of using a device of the present invention in combination with an active matrix substrate is briefly described with reference to FIG.  2 . 
     FIG. 2  illustrates an embodiment of panel structure comprising an EL device and drive means. The panel is provided with a scanning signal driver, a data signal driver and a current supply source which are connected to gate selection lines, data signal lines and current supply lines, respectively. At each intersection of the gate selection lines and the data signal lines, a display pixel electrode is disposed. The scanning signal drive sequentially selects the gate selection lines G1, G2, G3 . . . Gn, and in synchronism herewith, picture signals are supplied from the data signal driver to display a picture (image). 
   By driving a display panel including a luminescence layer comprising a luminescence material of the present invention, it becomes possible to provide a display which exhibits a good picture quality and is stable even for a long period display. 
   Some synthetic paths for providing a metal coordination compound represented by the above-mentioned formula (1) are illustrated below with reference to an iridium coordination compound (m+n=3) for example: 
                        
 
 
 
   Other metal coordination compound (M=Pt, Rh and Pd) can also be synthesized in a similar manner. 
   Some specific structural examples of metal coordination compounds used in the present invention are shown in Tables 1 to Tables 42 appearing hereinafter, which are however only representative examples and are not exhaustive. Pi to Cz for CyN1, CyN2, CyC1 and CyC2 shown in Tables 1 to 42 represent partial structures shown below. 
                        
                         
 
 
 
   Further, aromatic group Ph2 to DBT3 as substituents for CyN1, CyN2, CyC1 and CyC2 shown in Tables 1 to 42 represent partial structures shown below, with the proviso that substituents R5 to R8 of the aromatic groups represent hydrogen atoms when they are not specifically indicated. 
                        
                         
 
 
 
                                                                                                                                     TABLE 1                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                1   Ir   3   0   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —        2   Ir   3   0   Pi   FL1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —        3   Ir   3   0   Pi   FL1   —   —   CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —        4   Ir   3   0   Pi   FL1   —   —   H   CH 3     —   H   —   —                               —   —   H   H   —   —   —   —        5   Ir   3   0   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —        6   Ir   3   0   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —        7   Ir   3   0   Pi   FL1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —        8   Ir   3   0   Pi   FL1   —   —   H   FL6   H   H   H   —                               —   —   H   H   —   —   —   —        9   Ir   3   0   Pi   FL1   —   —   H   DBF2   H   H   H   —                               —   —   H   H   —   —   —   —       10   Ir   3   0   Pi   FL1   —   —   H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —       11   Ir   3   0   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       12   Ir   3   0   Pi   FL1   —   —   H   Ph2   H   C 3 H 7     H   H                               —   —   H   H   —   —   —   —       13   Ir   3   0   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       14   Ir   3   0   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       15   Ir   3   0   Pi   FL1   —   —   H   Tn7   H   H   —   —                               —   —   H   H   —   —   —   —       16   Ir   3   0   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 2                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               17   Ir   3   0   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       18   Ir   3   0   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       19   Ir   3   0   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —       20   Ir   3   0   Pi   Ph1   —   —   H   H   —   —   —   —                               C 2 H 5     C 2 H 5     FL5   H   H   H   H   —       21   Ir   3   0   Pi   Ph1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       22   Ir   3   0   Pi   Np2   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       23   Ir   3   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       24   Ir   3   0   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       25   Ir   3   0   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       26   Ir   3   0   Pi   FL2   CH 3     CH 3     H   CH 3     —   —   —   —                               —   —   H   H   —   —   —   —       27   Ir   3   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —       28   Ir   3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       29   Ir   3   0   Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       30   Ir   3   0   Pi   FL2   C 4 H 9     C 4 H 9     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       31   Ir   3   0   Pi   FL2   C 5 H 11     C 5 H 11     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       32   Ir   3   0   Pi   FL2   C 6 H 13     C 6 H 13     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 3                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               33   Ir   3   0   Pi   FL2   C 7 H 15     C 7 H 15     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       34   Ir   3   0   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       35   Ir   3   0   Pi   FL2   C 10 H 21     C 10 H 21     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       36   Ir   3   0   Pi   FL2   C 15 H 31     C 15 H 31     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —       37   Ir   3   0   Pi   FL2   C 20 H 41     C 20 H 41     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       38   Ir   3   0   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       39   Ir   3   0   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       40   Ir   3   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       41   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       42   Ir   3   0   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       43   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       44   Ir   3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —       45   Ir   3   0   Pi   FL2   C 5 H 11     C 5 H 11     H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       46   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               C 8 H 17     C 8 H 17     H   H   —   —   —   —       47   Ir   3   0   Pi   FL2   C 15 H 31     C 15 H 31     H   FL5   H   H   H   —                               C 15 H 31     C 15 H 31     H   H   —   —   —   —       48   Ir   3   0   Pi   FL2   Ph3   Ph3   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 4                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               49   Ir   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —       50   Ir   3   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       51   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL6   H   H   H   —                               —   —   H   H   —   —   —   —       52   Ir   3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   DBF2   H   H   H   —                               —   —   H   H   —   —   —   —       53   Ir   3   0   Pi   FL2   CH 3     CH 3     H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —       54   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       55   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   CF 3     H   H   H                               —   —   H   H   —   —   —   —       56   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —       57   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —       58   Ir   3   0   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                               —   —   H   H   —   —   —   —       59   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn6   H   H   —   —                               —   —   H   H   —   —   —   —       60   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                               —   —   H   H   —   —   —   —       61   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       62   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn7   H   H   —   —                               —   —   H   H   —   —   —   —       63   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn8   H   H   —   —                               —   —   H   H   —   —   —   —       64   Ir   3   0   Pi   FL2   CH 3     CH 3     H   An   H   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 5                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               65   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Pe2   H   —   —   —                               —   —   H   H   —   —   —   —       66   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Pi2   H   H   —   —                               —   —   H   H   —   —   —   —       67   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Pi3   H   H   —   —                               —   —   H   H   —   —   —   —       68   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Qn2   H   H   —   —                               —   —   H   H   —   —   —   —       69   Ir   3   0   Pi   FL2   Ph3   Ph3   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       70   Ir   3   0   Pi   FL2   CH 3     Ph3   H   An   H   —   —   —                               —   —   H   H   —   —   —   —       71   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       72   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       73   Ir   3   0   Pi   FL2   Ph3   Ph3   H   FL5   H   Ph3   H   —                               Ph3   Ph3   H   Ph2   H   H   H   H       74   Ir   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   Ph3   H   —                               CH 3     Ph3   H   Ph2   H   H   H   H       75   Ir   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   Ph3   H   —                               CH 3     Ph3   H   Ph2   H   H   H   H       76   Ir   3   0   Pi   FL2   (CH 2 ) 3 Ph3   (CH 2 ) 3 Ph3   H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       77   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn5   C 3 H 7     H   —   —       78   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn6   H   H   —   —       79   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Np3   H   H   —   —       80   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Np4   H   —   —   —                    
 
 
                                                                                                                                     TABLE 6                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               81   Ir   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   Ph3   H   —                               CH 3     Ph3   H   Tn7   H   H   —   —       82   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —       83   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   An   H   —   —   —       84   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Pe2   H   —   —   —       85   Ir   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   Ph3   H   —                               CH 3     Ph3   H   Pi2   C 2 H 5     H   —   —       86   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Pi3   H   H   —   —       87   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Qn2   H   H   —   —       88   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   DBT3   H   H   —   —       89   Ir   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       90   Ir   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       91   Ir   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   CF3   —   —   —   —       92   Ir   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —       93   Ir   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —       94   Ir   3   0   Pi   Tn1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       95   Ir   3   0   Pi   Tn2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       96   Ir   3   0   Pi   Tn3   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 7                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                97   Ir   3   0   Pi   Tn4   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —        98   Ir   3   0   Pi   Np1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —        99   Ir   3   0   Pi   Np2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       100   Ir   3   0   Pi   Pe1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       101   Ir   3   0   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —       102   Ir   3   0   Pi   Pe2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       103   Ir   3   0   Pi   Cn1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   —   —   —   —   —       104   Ir   3   0   Pi   Cn2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   —   —   —   —   —       105   Ir   3   0   Pi   FL3   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       106   Ir   3   0   Pi   DBF1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       107   Ir   3   0   Pi   DBT1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       108   Ir   3   0   Pi   Qn1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       109   Ir   3   0   Pi   Qn2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       110    Ir   3   0   Pi   Cz   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     Ph3   H   —   —   —   —       111   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       112   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn5   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 8                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               113   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn6   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       114   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Np3   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       115   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Np4   FL5   —   —   —                               CH 3     CH 3     H   H   —   —   —   —       116   Ir   3   0   Pi   FL2   Ph3   Ph3   H   Tn7   FL5   H   —   —                               Ph3   Ph3   H   H   —   —   —   —       117   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn8   FL5   H   —   —                               Ph3   Ph3   H   H   —   —   —   —       118   Ir   3   0   Pi   FL2   CH 3     CH 3     H   An   FL5   —   —   —                               CH 3     CH 3     H   H   —   —   —   —       119   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Pe2   FL5   —   —   —                               CH 3     CH 3     H   H   —   —   —   —       120   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Qn2   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       121   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL4   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       122   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       123   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL6   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       124   Ir   3   0   Pi   FL2   CH 3     CH 3     H   DBF2   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       125   Ir   3   0   Pi   FL2   CH 3     CH 3     H   DBF3   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       126   Ir   3   0   Pi   FL2   CH 3     CH 3     H   DBT2   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       127   Ir   3   0   Pi   FL2   CH 3     CH 3     H   DBT3   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       128   Ir   3   0   Pi   Ph1   —   —   H   H   —   —   —   —                               C 8 H 17     C 8 H 17     FL5   H   H   H   H   —                    
 
 
                                                                                                                                                                                               TABLE 9                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R′″   CyC1-R3   CyC1-R4   R5   R6   R7   R8                    129   Ir   3   0   Pi   Tn1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       130   Ir   3   0   Pi   Tn2   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       131   Ir   3   0   Pi   Tn3   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       132   Ir   3   0   Pi   Tn4   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       133   Ir   3   0   Pi   Np2   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       134   Ir   3   0   Pi   Pe1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       135   Ir   3   0   Pi   Cn1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   —   H   H   H   —       136   Ir   3   0   Pi   Cn2   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   —   H   H   H   —       137   Ir   3   0   Pi   FL3   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       138   Ir   3   0   Pi   DBF1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       139   Ir   3   0   Pi   DBT1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       140   Ir   3   0   Pi   Qn1   —   —   H   H   —   —   —   —                               CH 3     Ph3   FL5   H   H   H   H   —       141   Ir   3   0   Pi   Qn2   —   —   H   H   —   —   —   —                               C 5 H 11     C 5 H 11     FL5   H   H   H   H   —       142   Ir   3   0   Pi   Cz   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       143   Ir   3   0   Pi   Ph1   —   —   H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       144   Ir   3   0   Pi   FL3   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 10                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               145   Ir   3   0   Pi   FL3   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       146   Ir   3   0   Pi   DBF1   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       147   Ir   3   0   Pi   DBT1   CH 3     CH 3     H   CH 3     —   —   —   —                               —   —   H   H   —   —   —   —       148   Ir   3   0   Pi   FL3   —   —   H   FL6   H   H   H   —                               —   —   H   H   —   —   —   —       149   Ir   3   0   Pi   DBF1   —   —   H   DBF2   H   H   H   —                               —   —   H   H   —   —   —   —       150   Ir   3   0   Pi   DBT1   —   —   H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —       151   Rh   3   0   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       152   Rh   3   0   Pi   FL1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       153   Rh   3   0   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       154   Rh   3   0   Pi   FL1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       155   Rh   3   0   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       156   Rh   3   0   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       157   Rh   3   0   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       158   Rh   3   0   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       159   Rh   3   0   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       160   Rh   3   0   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 11                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               161   Rh   3   0   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —       162   Rh   3   0   Pi   Ph1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       163   Rh   3   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       164   Rh   3   0   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       165   Rh   3   0   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       166   Rh   3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       167   Rh   3   0   Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       168   Rh   3   0   Pi   FL2   C 4 H 9     C 4 H 9     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       169   Rh   3   0   Pi   FL2   C 5 H 11     C 5 H 11     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       170   Rh   3   0   Pi   FL2   C 6 H 13     C 6 H 13     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       171   Rh   3   0   Pi   FL2   C 15 H 31     C 15 H 31     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —       172   Rh   3   0   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       173   Rh   3   0   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       174   Rh   3   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       175   Rh   3   0   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       176   Rh   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                    
 
 
                                                                                                                                                                                               TABLE 12                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                    177   Rh    3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —       178   Rh   3   0   Pi   FL2   C 5 H 11     C 5 H 11     H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       179   Rh   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               C 8 H 17     C 8 H 17     H   H   —   —   —   —       180   Rh   3   0   Pi   FL2   C 15 H 31     C 15 H 31     H   FL5   H   H   H   —                               C 15 H 31     C 15 H 31     H   H   —   —   —   —       181   Rh   3   0   Pi   FL2   Ph3   Ph3   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —       182   Rh   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —       183   Rh   3   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       184   Rh   3   0   Pi   FL2   CH 3     CH 3     H   FL6   H   H   H   —                               —   —   H   H   —   —   —   —       185   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       186   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   CF 3     H   H   H                               —   —   H   H   —   —   —   —       187   Rh   3   0   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                               —   —   H   H   —   —   —   —       188   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                               —   —   H   H   —   —   —   —       189   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       190   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Tn8   H   H   —   —                               —   —   H   H   —   —   —   —       191   Rh   3   0   Pi   FL2   CH 3     CH 3     H   An   H   —   —   —                               —   —   H   H   —   —   —   —       192   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Pe2   H   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 13                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               193   Rh   3   0   Pi   FL2   CH 3     CH 3     H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       194   Rh   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       195   Rh   3   0   Pi   FL2   Ph3   Ph3   H   FL5   H   Ph3   H   —                               Ph3   Ph3   H   Ph2   H   H   H   H       196   Rh   3   0   Pi   FL2   CH 3     Ph3   H   FL5   H   Ph3   H   —                               CH 3     Ph3   H   Ph2   H   H   H   H       197   Rh   3   0   Pi   FL2   (CH 2 ) 3 Ph3   (CH 2 ) 3 Ph3   H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       198   Rh   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn5   C 3 H 7     H   —   —       199   Rh   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       200   Rh   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       201   Rh   3   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   CF3   —   —   —   —       202   Rh   3   0   Pi   Tn4   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       203   Rh   3   0   Pi   Np2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       204   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       205   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Tn5   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       206   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Tn6   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       207   Rh   3   0   Pi   FL2   CH 3     CH 3     H   Np3   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       208   Rh   3   0   Pi   Ph1   —   —   H   H   —   —   —   —                               C 8 H 17     C 8 H 17     FL5   H   H   H   H   —                    
 
 
                                                                                                                                     TABLE 14                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               209   Rh   3   0   Pi   Tn1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       210   Rh   3   0   Pi   Ph1   —   —   H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       211   Pt   2   0   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       212   Pt   2   0   Pi   FL1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       213   Pt   2   0   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       214   Pt   2   0   Pi   FL1   —   —   H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —       215   Pt   2   0   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       216   Pt   2   0   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       217   Pt   2   0   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       218   Pt   2   0   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       219   Pt   2   0   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       220   Pt   2   0   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       221   Pt   2   0   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —       222   Pt   2   0   Pi   Ph1   —   —   H   H   —   —   —   —                               C 2 H 5     C 2 H 5     FL5   H   H   H   H   —       223   Pt   2   0   Pi   Np2   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       224   Pt   2   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 15                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               225   Pt   2   0   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       226   Pt   2   0   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       227   Pt   2   0   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       228   Pt   2   0   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       229   Pt   2   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       230   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       231   Pt   2   0   Pi   FL2   C 5 H 11     C 5 H 11     H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       232   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               C 8 H 17     C 8 H 17     H   H   —   —   —   —       233   Pt   2   0   Pi   FL2   Ph3   Ph3   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —       234   Pt   2   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       235   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       236   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   CF 3     H   H   H                               —   —   H   H   —   —   —   —       237   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —       238   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —       239   Pt   2   0   Pi   FL2   CH 3     Ph3   H   An   H   —   —   —                               —   —   H   H   —   —   —   —       240   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H                    
 
 
                                                                                                                                     TABLE 16                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               241   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       242   Pt   2   0   Pi   FL2   Ph3   Ph3   H   FL5   H   Ph3   H   —                               Ph3   Ph3   H   Ph2   H   H   H   H       243   Pt   2   0   Pi   FL2   (CH 2 ) 3 Ph3   (CH 2 ) 3 Ph3   H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       244   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn5   C 3 H 7     H   —   —       245   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   DBT3   H   H   —   —       246   Pt   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       247   Pt   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       248   Pt   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   CF3   —   —   —   —       249   Pt   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —       250   Pt   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —       251   Pt   2   0   Pi   Tn1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       252   Pt   2   0   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —       253   Pt   2   0   Pi   Pe2   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       254   Pt   2   0   Pi   Cn1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   —   —   —   —   —       255   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       256   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Tn5   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 17                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               257   Pt   2   0   Pi   FL2   CH 3     CH 3     H   Tn6   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       258   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL4   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       259   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL5   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       260   Pt   2   0   Pi   FL2   CH 3     CH 3     H   FL6   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       261   Pt   2   0   Pi   FL2   CH 3     CH 3     H   DBF2   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       262   Pt   2   0   Pi   FL2   CH 3     CH 3     H   DBF3   FL5   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       263   Pt   2   0   Pi   Ph1   —   —   H   H   —   —   —   —                               C 8 H 17     C 8 H 17     FL5   H   H   H   H   —       264   Pt   2   0   Pi   Tn1   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       265   Pt   2   0   Pi   Tn2   —   —   H   H   —   —   —   —                               CH 3     CH 3     FL5   H   H   H   H   —       266   Pt   2   0   Pi   Ph1   —   —   H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       267   Pt   2   0   Pi   FL3   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       268   Pt   2   0   Pi   FL3   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       269   Pt   2   0   Pi   DBF1   —   —   CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       270   Pt   2   0   Pi   DBT1   —   —   H   CH 3     —   —   —   —                               —   —   H   H   —   —   —   —       271   Pd   2   0   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       272   Pd   2   0   Pi   FL1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 18                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               273   Pd   2   0   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       274   Pd   2   0   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —       275   Pd   2   0   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       276   Pd   2   0   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —       277   Pd   2   0   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       278   Pd   2   0   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —       279   Pd   2   0   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       280   Pd   2   0   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —       281   Pd   2   0   Pi   Np2   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —       282   Pd   2   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       283   Pd   2   0   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       284   Pd   2   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       285   Pd   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       286   Pd   2   0   Pi   FL2   C 5 H 11     C 5 H 11     H   FL5   H   H   H   —                               CH 5 H 11     CH 5 H 11     H   H   —   —   —   —       287   Pd   2   0   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       288   Pd   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                     TABLE 19                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8               289   Pd   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   CF 3     H   H   H                               —   —   H   H   —   —   —   —       290   Pd   2   0   Pi   FL2   CH 3     CH 3     H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H       291   Pd   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H       292   Pd   2   0   Pi   FL2   Ph3   Ph3   H   FL5   H   Ph3   H   —                               Ph3   Ph3   H   Ph2   H   H   H   H       293   Pd   2   0   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   DBT3   H   H   —   —       294   Pd   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —       295   Pd   2   0   Pi   Ph1   —   —   H   FL5   H   H   H   —                               C 5 H 11     C 5 H 11     H   H   —   —   —   —       296   Pd   2   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       297   Pd   2   0   Pi   FL2   CH 3     CH 3     H   Tn5   FL5   H   —   —                               CH 3     CH 3     H   H   —   —   —   —       298   Pd   2   0   Pi   Ph1   —   —   H   H   —   —   —   —                               C 8 H 17     C 8 H 17     FL5   H   H   H   H   —       299   Pd   2   0   Pi   Ph1   —   —   H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —       300   Pd   2   0   Pi   DBT1   —   —   H   CH 3     —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 20                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               301   Ir   2   1   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       302   Ir   2   1   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       303   Ir   2   1   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       304   Ir   2   1   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       305   Ir   2   1   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       306   Ir   2   1   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       307   Ir   2   1   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       308   Ir   2   1   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       309   Ir   2   1   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       310   Ir   2   1   Pi   Ph1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 21                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               311   Ir   2   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       312   Ir   2   1   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       313   Ir   2   1   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       314   Ir   2   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       315   Ir   2   1   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       316   Ir   2   1   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       317   Ir   2   1   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       318   Ir   2   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       319   Ir   2   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       320   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 22                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               321   Ir   2   1   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —                       Pr   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       322   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pr   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       323   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                       Py1   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       324   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                       Py2   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       325   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CH 3     H   —   —   —   —       326   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Br   H   —   —   —   —       327   Ir   2   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CF 3     H   —   —   —   —       328   Ir   2   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   C 5 H 11     H   —   —   —   —       329   Ir   2   1   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   OCH 3     H   —   —   —   —       330   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 23                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               331   Ir   2   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       332   Ir   2   1   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       333   Ir   2   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                       Pi   Tn2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       334   Ir   2   1   Pi   FL2   C 4 H 9     C 4 H 9     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn3   —   —   H   H   —   —   —   —                               —   —   H   CH 3     —   —   —   —       335   Ir   2   1   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn4   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       336   Ir   2   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Np1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       337   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Np2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       338   Ir   2   1   Pi   FL2   C 15 H 31     C 15 H 31     H   FL5   H   H   H   —                               C 15 H 31     C 15 H 31     H   H   —   —   —   —                       Pi   Pe1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       339   Ir   2   1   Pi   FL2   CH 3     Ph3   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —                       Pi   Cn1   —   —   H   H   —   —   —   —                               —   —   H   —   —   —   —   —       340   Ir   2   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Cn2   —   —   H   H   —   —   —   —                               —   —   H   —   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 24                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               341   Ir   2   1   Pi   FL2   CH 3     CH 3     H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       342   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       343   Ir   2   1   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       344   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       345   Ir   2   1   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       346   Ir   2   1   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       347   Ir   2   1   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL3   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       348   Ir   2   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   DBF1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       349   Ir   2   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   DBT1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       350   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Qn1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 25                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               351   Ir   2   1   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —                       Pr   Qn2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       352   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pr   Cz   —   —   H   H   —   —   —   —                               —   —   Ph3   H   —   —   —   —       353   Rh   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       354   Rh   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                       Py2   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       355   Rh   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CH 3     H   —   —   —   —       356   Rh   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Br   H   —   —   —   —       357   Rh   2   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CF 3     H   —   —   —   —       358   Rh   2   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   C 5 H 11     H   —   —   —   —       359   Rh   2   1   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   OCH 3     H   —   —   —   —       360   Rh   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 26                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               361   Ir   1   2   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       362   Ir   1   2   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       363   Ir   1   2   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       364   Ir   1   2   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       365   Ir   1   2   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       366   Ir   1   2   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       367   Ir   1   2   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       368   Ir   1   2   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       369   Ir   1   2   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       370   Ir   1   2   Pi   Ph1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 27                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               371   Ir   1   2   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       372   Ir   1   2   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       373   Ir   1   2   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       374   Ir   1   2   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       375   Ir   1   2   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       376   Ir   1   2   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       377   Ir   1   2   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       378   Ir   1   2   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       379   Ir   1   2   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       380   Ir   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 28                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               381   Ir   1   2   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —                       Pr   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       382   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pr   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       383   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                       Py1   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       384   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                       Py2   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       385   Ir   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CH 3     H   —   —   —   —       386   Ir   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Br   H   —   —   —   —       387   Ir   1   2   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CF 3     H   —   —   —   —       388   Ir   1   2   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   C 5 H 11     H   —   —   —   —       389   Ir   1   2   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   OCH 3     H   —   —   —   —       390   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 29                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               391   Ir   1   2   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       392   Ir   1   2   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       393   Ir   1   2   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                       Pi   Tn2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       394   Ir   1   2   Pi   FL2   C 4 H 9     C 4 H 9     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn3   —   —   H   H   —   —   —   —                               —   —   H   CH 3     —   —   —   —       395   Ir   1   2   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn4   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       396   Ir   1   2   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Np1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       397   Ir   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Np2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       398   Ir   1   2   Pi   FL2   C 15 H 31     C 15H   31     H   FL5   H   H   H   —                               C 15 H 31     C 15 H 31     H   H   —   —   —   —                       Pi   Pe1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       399   Ir   1   2   Pi   FL2   CH 3     Ph3   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —                       Pi   Cn1   —   —   H   H   —   —   —   —                               —   —   H   —   —   —   —   —       400   Ir   1   2   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Cn2   —   —   H   H   —   —   —   —                               —   —   H   —   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 30                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               401   Ir   1   2   Pi   FL2   CH 3     CH 3     H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       402   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       403   Ir   1   2   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       404   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       405   Ir   1   2   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       406   Ir   1   2   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       407   Ir   1   2   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL3   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       408   Ir   1   2   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   DBF1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       409   Ir   1   2   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   DBT1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       410   Ir   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Qn1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 31                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               411   Ir   1   2   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —                       Pr   Qn2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       412   Ir   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pr   Cz   —   —   H   H   —   —   —   —                               —   —   Ph3   H   —   —   —   —       413   Rh   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       414   Rh   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                       Py2   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       415   Rh   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CH 3     H   —   —   —   —       416   Rh   1   2   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Br   H   —   —   —   —       417   Rh   1   2   Pi   Phi   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CF 3     H   —   —   —   —       418   Rh   1   2   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   C 5 H 11     H   —   —   —   —       419   Rh   1   2   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   OCH 3     H   —   —   —   —       420   Rh   1   2   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 32                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               421   Pt   1   1   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       422   Pt   1   1   Pi   FL1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       423   Pt   1   1   Pi   FL1   —   —   H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       424   Pt   1   1   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       425   Pt   1   1   Pi   FL1   —   —   H   Np4   H   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       426   Pt   1   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       427   Pt   1   1   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       428   Pt   1   1   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       429   Pt   1   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       430   Pt   1   1   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 33                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               431   Pt   1   1   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —                       Pr   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       432   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pr   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       433   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                       Py1   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       434   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                       Py2   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       435   Pt   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CH 3     H   —   —   —   —       436   Pt   1   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —       437   Pt   1   1   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       438   Pt   1   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                       Pi   Tn2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       439   Pt   1   1   Pi   FL2   C 4 H 9     C 4 H 9     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn3   —   —   H   H   —   —   —   —                               —   —   H   CH 3     —   —   —   —       440   Pt   1   1   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Tn4   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 34                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               441   Pt   1   1   Pi   FL2   CH 3     CH 3     H   DBT3   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       442   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       443   Pt   1   1   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       444   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       445   Pt   1   1   Pi   FL2   C 8 H 17     C 8 H 17     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       446   Pt   1   1   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                               C 2 H 5     C 2 H 5     H   H   —   —   —   —                       Pr   Qn2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       447   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                       Pr   Cz   —   —   H   H   —   —   —   —                               —   —   Ph3   H   —   —   —   —       448   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       449   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                       Py2   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       450   Pt   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CH 3     H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 35                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               451   Pt   1   1   Pi   Ph1   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       452   Pt   1   1   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       453   Pt   1   1   Pi   FL1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       454   Pt   1   1   Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   FL4   H   H   H   H   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       455   Pt   1   1   Pi   Ph1   —   —   H   Ph2   H   FL4   H   H                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       456   Pt   1   1   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       457   Pt   1   1   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       458   Pt   1   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       459   Pt   1   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       460   Pt   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 36                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               461   Pt   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Br   H   —   —   —   —       462   Pt   1   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CF 3     H   —   —   —   —       463   Pt   1   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   C 5 H 11     H   —   —   —   —       464   Pt   1   1   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   OCH 3     H   —   —   —   —       465   Pt   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —       466   Pd   1   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Np1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       467   Pd   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Np2   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       468   Pd   1   1   Pi   FL2   C 15 H 31     C 15 H 31     H   FL5   H   H   H   —                               C 15 H 31     C 15 H 31     H   H   —   —   —   —                       Pi   Pe1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       469   Pd   1   1   Pi   FL2   CH 3     Ph3   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —                       Pi   Cn1   —   —   H   H   —   —   —   —                               —   —   H   —   —   —   —   —       470   Pd   1   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Cn2   —   —   H   H   —   —   —   —                               —   —   H   —   —   —   —   —                    
 
 
                                                                                                                                                                                                                                             TABLE 37                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                CyN2                R   R′   CyN2-R1   CyN2-R2   R5   R6   R7   R8                CyC2            No   M   m   n   CyN2   CyC2   R″   R″′   CyC2-R3   CyC2-R4   R5   R6   R7   R8               471   Pd   1   1   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                               —   —   H   H   —   —   —   —       472   Pd   1   1   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   FL3   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       473   Pd   1   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                       Pi   DBF1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       474   Pd   1   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   DBT1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —       475   Pd   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Qn1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —       476   Pd   1   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Tn8   H   H   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Br   H   —   —   —   —       477   Pd   1   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   CF 3     H   —   —   —   —       478   Pd   1   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   C 5 H 11     H   —   —   —   —       479   Pd   1   1   Pi   Np2   —   —   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   OCH 3     H   —   —   —   —       480   Pd   1   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                       Pi   Ph1   —   —   H   H   —   —   —   —                               —   —   Cl   H   —   —   —   —                    
 
 
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                   TABLE 38                           CyN1                R   R′   CyN1—R1   CyN1—R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1—R3   CyC1—R4   R5   R6   R7   R8               481   Ir   3   0   Pi   FL1   —   —   H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            482   Ir   3   0   Pi   FL1   —   —   H   CF 3     —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            483   Ir   3   0   Pi   FL1   —   —   H   FL4   H   H   H   —                —   —   —CH═CH—CH═CH—   —   —   —   —            484   Ir   3   0   Pi   FL1   —   —   H   Ph2   H   H   H   H                —   —   —CH═CH—CH═CH—   —   —   —   —            485   Ir   3   0   Pi   FL1   —   —   H   FL4   H   Ph3   H   —                —   —   —CH═CH—CH═CH—   H   H   H   H            486   Ir   3   0   Pi   FL1   —   —   H   Np4   H   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            487   Ir   3   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            488   Ir   3   0   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            489   Ir   3   0   Pi   FL2   CH 3     CH 3     CF 3     CF 3     —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            490   Ir   3   0   Pi   FL2   CH 3     CH 3     H   CH 3     —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            491   Ir   3   0   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            492   Ir   3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            493   Ir   3   0   Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            494   Ir   3   0   Pi   FL2   C 4 H 9     C 4 H 9     H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            495   Ir   3   0   Pi   FL2   Ph3   Ph3   H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            496   Ir   3   0   Pi   FL2   CH 3     Ph3   H   H   —   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            497   Ir   3   0   Pi   FL2   H   H   H   FL5   H   H   H   —                CH 3     CH 3     —CH═CH—CH═CH—   —   —   —   —            498   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                CH 3     CH 3     —CH═CH—CH═CH—   —   —   —   —            499   Ir   3   0   Pi   FL2   C 2 H 5     C 2 H 5     H   FL5   H   H   H   —                C 2 H 5     C 2 H 5     —CH═CH—CH═CH—   —   —   —   —            500   Ir   3   0   Pi   FL2   C 5 H 11     C 5 H 11     H   FL5   H   H   H   —                C 5 H 11     C 5 H 11     —CH═CH—CH═CH—   —   —   —   —            501   Ir   3   0   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                C 8 H 17     C 8 H 17     —CH═CH—CH═CH—   —   —   —   —            502   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                —   —   —CH═CH—CH═CH—   —   —   —   —                        
 
 
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                           TABLE 39                           CyN1                R   R′   CyN1—R1   CyN1—R2   R5   R6   R7   R8                CyC1            No   M   m   n   CyN1   CyC1   R″   R″′   CyC1—R3   CyC1—R4   R5   R6   R7   R8               503   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   CF 3     H   H   H                —   —   —CH═CH—CH═CH—   —   —   —   —            504   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                —   —   —CH═CH—CH═CH—   —   —   —   —            505   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                —   —   —CH═CH—CH═CH—   —   —   —   —            506   Ir   3   0   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            507   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn6   H   H   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            508   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            509   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Np4   H   —   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —            510   Ir   3   0   Pi   FL2   CH 3     CH 3     H   Tn7   H   H   —   —                —   —   —CH═CH—CH═CH—   —   —   —   —                        
 
 
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         TABLE 40                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                E                E   R″   R″′       R5   R6   R7   R8                G            No   M   m   n   G   R″   R″′           R5   R6   R7   R8                    511   Ir   2   1   Pi   FL1   —   —   H   H   —   —   —   —                               —   —   H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —            512   Ir   2   1   Pi   FL1   —   —   H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                CF 3     —   —       —   —   —   —           CF 3     —   —       —   —   —   —            513   Ir   2   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —            514   Ir   2   1   Pi   FL2   CH 3     CH 3     H   CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                Ph2   —   —        H   H   H   H           Ph2   —   —       H   H   H   H            515   Ir   2   1   Pi   FL2   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   OC 4 H 9     —   —   —   —                Ph2   —   —       H   C 3 H 7     H   H           Ph2   —   —       H   C 3 H 7     H   H            516   Ir   2   1   Pi   FL2   C 6 H 13     C 6  H 13     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                CH 3     —   —       —   —   —   —           FL5   CH 3     CH 3         H   H   H   —            517   Ir   2   1   Pi   FL2   H   H   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                Tn5   —   —       H   H   —   —           Tn5   —   —       H   H   —   —            518   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                Tn6   —   —       H   H   —   —           Tn6   —   —       H   H   —   —            519   Ir   2   1   Pi   FL2   Ph3   Ph3   H   FL5   H   H   H   —                               Ph3   Ph3   H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —            520   Ir   2   1   Pi   FL2   CH 3     Ph3   H   FL5   H   H   H   —                               CH 3     Ph3   H   H   —   —   —   —                CF 3     —   —       —   —   —   —           CF 3     —   —       —   —   —   —                        
 
 
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         TABLE 41                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                E                E   R″   R″′       R5   R6   R7   R8                G            No   M   m   n   G   R″   R″′           R5   R6   R7   R8                    521   Ir   2   1   Pi   FL2   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                NP3   —   —       CH 3 O   H   —   —           NP3   —   —       CH 3 O   H   —   —            522   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   H   H   H                               —   —   H   H   —   —   —   —                NP4   —   —       F   —   —   —           NP4   —   —       F   —   —   —            523   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OCH 2 C 5 F 11     H   H                               —   —   H   H   —   —   —   —                Tn7   —   —       CH 3     —   —   —           Tn7   —   —       CH 3     —   —   —            524   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   OC≡C—C 7 H 15     H   H                               —   —   H   H   —   —   —   —                Tn8   —   —       H   —   —   —           Tn8   —   —       H   —   —   —            525   Ir   2   1   Pi   FL2   C 3 H 7     C 3 H 7     H   Tn5   H   H   —   —                               —   —   H   H   —   —   —   —                Pe2   —   —       H   —   —   —           Pe2   —   —       H   —   —   —            526   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL4   H   Ph3   H   —                               —   —   H   Ph2   H   H   H   H                Pi2   —   —       H   H   —   —           Pi2   —   —       H   H   —   —            527   Ir   2   1   Pi   FL2   CH 3     CH 3     H   FL5   H   Ph3   H   —                               CH 3     CH 3     H   Ph2   H   H   H   H                Pi3   —   —       CH 3     CH 3     H   H           Pi3   —   —       CH 3     CH 3     H   H            528   Ir   2   1   Pi   Ph1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                FL4   —   —       H   H   H   —           FL4   —   —       H   H   H   —            529   Ir   2   1   Pi   FL2   CH 3     CH 3     H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                FL5   C 2 H 5     C 2 H 5         H   H   H   —           FL5   (CH 2 ) 5 Ph3   (CH 2 ) 5 Ph3       H   H   H   —            530   Ir   2   1   Pi   Ph1   —   —   H   H   —   —   —   —                               C 8 H 17     C 8 H 17     FL5   H   H   H   H   —                DBF2   —   —       H   H   H   —           DBF2   —   —       H   H   H   —                        
 
 
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                         TABLE 42                           CyN1                R   R′   CyN1-R1   CyN1-R2   R5   R6   R7   R8                CyC1                CyN1   CyC1   R″   R″′   CyC1-R3   CyC1-R4   R5   R6   R7   R8                E                E   R″   R″′       R5   R6   R7   R8                G            No   M   m   n   G   R″   R″′           R5   R6   R7   R8                    531   Ir   2   1   Pi   Ph1   —   —   H   Ph2   H   FL5   H   H                               CH 3     CH 3     H   H   —   —   —   —                DBT3   —   —       H   H   H   —           DBT3   —   —       H   H   H   —            532   Rh   2   1   Pi   FL3   CH 3     CH 3     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —            533   Rh   2   1   Pi   DBF1   CH 3     CH 3     CF 3     CF 3     —   —   —   —                               —   —   H   H   —   —   —   —                CF 3     —   —       —   —   —   —           CF 3     —   —       —   —   —   —            534   Rh   2   1   Pi   FL1   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                Qn2   —   —       H   H   —   —           Qn2   —   —       H   H   —   —            535   Rh   2   1   Pi   Np2   —   —   H   FL4   H   H   H   —                               —   —   H   H   —   —   —   —                Np3   —   —       H   H   —   —           Np3   —   —       H   H   —   —            536   Pt   1   1   Pi   FL2   C 3 H 7     C 3 H 7     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —            537   Pt   1   1   Pi   FL2   C 5 H 11     C 5 H 11     H   H   —   —   —   —                               —   —   H   H   —   —   —   —                CF 3     —   —       —   —   —   —           CF 3     —   —       —   —   —   —            538   Pd   1   1   Pi   FL2   C 15 H 31     C 15 H 31     H   FL5   H   H   H   —                               C 15 H 31     C 15 H 31     H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —            539   Pd   1   1   Pi   FL2   CH 3     CH 3     H   Np3   H   H   —   —                               —   —   H   H   —   —   —   —                CF 3     —   —       —   —   —   —           CF 3     —   —       —   —   —   —            540   Ir   1   2   Pi   Tn4   —   —   H   FL5   H   H   H   —                               CH 3     CH 3     H   H   —   —   —   —                CH 3     —   —       —   —   —   —           CH 3     —   —       —   —   —   —                        
 
 
   Hereinbelow, the present invention will be described more specifically based on Examples. 
   EXAMPLE 1 
   Synthesis of Example Compound No. 23 
                              
 
 
   In a 30 liter-three-necked flask, 307.3 g (960 mM) of 2-iodo-9,9-dimethylfluorene and 10 liters of dry THF (tetrahydrofuran) were placed and cooled to −72 to 70° C. under stirring in an argon gas stream atmosphere. To the mixture, a 1.6M solution of n-butyllithium in hexane was added dropwise in 1 hour, followed by further stirring for 2 hours at the temperature. Thereafter, under stirring at −73 to −71° C., to the system, a solution of 209.5 g (2016 mM) of trimethyl borate in 1.3 liters of dry THT was added dropwise in 2 hours. The reaction mixture was left standing overnight on an ice water bath. To the mixture, 1.6 liters of 4N-hydrochloric acid was added in 0.5 hour at 0-7° C., followed by stirring for 1 hour at room temperature and extraction with toluene. The organic layer was washed with saturated saline water, followed by distilling-off of the solvent under a reduced pressure to obtain a residue. To the residue, hexane was added and heated under heating, followed by cooling to precipitate a crystal. The crystal was recovered by filtration and purified by silica gel column chromatography (eluent: toluene/ethyl acetate=1/1), followed by successive recrystallization from a chloroform-hexane mixture solvent, toluene, an ethyl acetate-toluene-THF mixture solvent, and toluene to obtain 32.0 g of 2-(9,9-dimethylfluorenyl)boronic acid (colorless crystal) (Yield: 14.0%). 
                        
 
 
 
   In a 300 ml-three-necked flask, 8.5 g (53.8 mM) of 2-bromopyridine, 12.8 g (53.8 mM) of 2-(9,9-dimethylfluorenyl)boronic acid, 55 ml of toluene, 27 ml of ethanol and 55 ml of 2M-sodium carbonate aqueous solution were placed and stirred at room temperature under nitrogen stream, and 1.97 g (1.70 mM) of tetrakis(triphenylphosphine)palladium (0) was added thereto. Thereafter, reflux under stirring for 5.5 hours was performed under nitrogen stream. After the reaction, the reaction mixture was cooled and extracted by addition of cold water and toluene. The organic layer was washed with water until neutrality, and the solvent was removed under reduced pressure to obtain a residue. The residue was successively purified by silica gel column chromatography (eluent: toluene/THF=10/1) and that (eluent: hexane/ethyl acetate=8/1) to obtain 12.2 g of 2-{2-(9,9-dimethylfluorenyl)}pyridine (pale brown viscous liquid) (Yield: 83.6%). 
                        
 
 
 
   In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heated at 130-140° C. under stirring and bubbling with nitrogen for 2 hours. Then, the glycerol was cooled by standing down to 100° C., and 1.69 g (6.23 mM) of 2-{2-(9,9-dimethylfluorenyl)}pyridine and 0.50 g (1.02 mM) of iridium (III) acetylacetonate were added, followed by 5 hours of heating at 176-219° C. under stirring and nitrogen stream. The reaction product was cooled to room temperature and injected into 300 ml of 1N-hydrochloric acid to form a precipitate, which was filtered out and washed with water, followed by drying for 5 hours at 100° C. under reduced pressure. The precipitate was purified by silica gel column chromatography with chloroform as the eluent to obtain 0.17 g (yield=21.3%) of orange powdery tris[2-(9,9-dimethylfluorene-2-yl)pyridine-C 3 ,N]iridium (III). According to MALDI-TOF MS (matrix-assisted laser desorption ionization-time of fight mass spectroscopy), the compound exhibited M + (mass number of the corresponding cation formed by removal of 1 electron) of 1003.4. 
   A toluene solution of the compound exhibited a photoluminescence spectrum showing λmax (maximum emission wavelength)=545 nm and a quantum yield of 0.23. 
   The compound (Ex. Comp. No. 23) exhibited better synthesis yield and quantum yield, thus being most suitable luminescence material in the present invention. 
   EXAMPLE 2 
   Synthesis of Example Compound No. 43 
                              
 
 
   In a 100 ml-three-necked flask, 1.18 g (4.98 mM) of 2,5-dibromopyridine, 3.57 g (15.0 mM) 2-(9,9-dimethylfluorenyl)boronic acid prepared in Example 1, 10 ml of toluene, 5 ml of ethanol and 10 ml of 2M-sodium carbonate aqueous solution were placed and stirred at room temperature under nitrogen stream, and 0.35 g (0.30 mM) of tetrakis(triphenylphosphine)-palladium (0) was added thereto. Thereafter, reflux under stirring was performed for 12 hours under nitrogen stream. After completion of the reaction, the reaction product was cooled on an ice bath to precipitate a crystal, which was then filtered out and washed with water. To the crystal, 100 ml of methanol was added and washed at room temperature under stirring, and then was recovered by filtration. The resultant crystal was purified by silica gel column chromatography (eluent: chloroform) to obtain 2.10 g (yield=91.0%) of 2,5-bis{2-(9,9-dimethyl-fluorenyl)}pyridine (colorless crystal). 
                        
 
 
 
   In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heated at 130-140° C. under stirring and bubbling with nitrogen for 2 hours. Then, the glycerol was cooled by standing down to 100° C., and 1.85 g (3.99 mM) of 2,5-bis{2-(9,9-dimethylfluorenyl)}pyridine and 0.40 g (0.82 mM) of iridium (III) acetylacetonate were added, followed by 5 hours of reflux at 180-235° C. under stirring and nitrogen stream. The reaction product was cooled to room temperature and injected into 300 ml of 1N-hydrochloric acid to form a precipitate, which was filtered out and washed with water, followed by drying for 5 hours at 100° C. under reduced pressure. The precipitate was purified by silica gel column chromatography with chloroform as the eluent and recrystallized from a chloroform-methanol mixture solvent to obtain 0.10 g (yield=7.7%) of red powdery tris[2,5-bis(9,9-dimethylfluorene-2-yl)pyridine-C 3 ,N]iridium (III). According to MALDI-TOF MS, the compound exhibited M +  of 1589.6. 
   A toluene solution of the compound exhibited a photoluminescence spectrum showing λmax=591 nm and a quantum yield of 0.12. 
   EXAMPLES 3-11 
   Each of luminescence devices having a layer structure shown in  FIG. 1B  were prepared in the following manner. 
   On a 1.1 mm-thick glass substrate (transparent substrate  15 ), a 100 nm-thick film (transparent electrode  14 ) of ITO (indium tin oxide) was formed by sputtering, followed by patterning to form a stripe electrode including 100 lines each having a width of 100 nm and a spacing with an adjacent line of 10 nm (i.e., electrode pitch of 110 nm). 
   On the ITO-formed substrate, three organic layers and two metal electrode layers shown below were successively formed by vacuum (vapor) deposition using resistance heating in a vacuum chamber (10 −4  Pa).
         Organic layer 1 (hole transport layer  13 ) (40 nm): α-NPD   Organic layer 2 (luminescence layer  12 ) (30 nm): co-deposited film of CBP:metal complex (metal coordination compound shown in Table 45) (95:5 by weight)   Organic layer 3 (electron transport layer  16 ) (30 nm): Alq3   Metal electrode layer 1 (metal electrode  11 ) (15 nm): Al—Li alloy (Li=1.8 wt. %)   Metal electrode layer 2 (metal electrode  11 ) (100 nm): Al       

   The above-deposited metal electrode layers 1 and 2 (Al—Li layer and Al layer) had a stripe electrode pattern including 100 lines each having a width of 100 nm and a spacing of 10 nm (electrode pitch=110 nm) and arranged so that the stripe electrode pattern intersected with that of the ITO electrode at right angles to form a matrix of pixels each having an effective electrode area of 3 mm 2  comprising 20 ITO lines bundled together at a lead-out portion and 15 Al (Al—Li) lines bundled together at a lead-out portion. 
   Each of the thus-prepared luminescence devices was taken out of the vacuum chamber and was subjected to a continuous energization (current passage) test in an atmosphere of dry nitrogen gas stream so as to remove device deterioration factors, such as oxygen and moisture (water content). 
   The continuous energization test was performed by continuously applying a voltage at a constant current density of 70 mA/cm 2  to the luminescence device having the ITO (transparent) electrode (as an anode) and the Al (metal) electrode (as a cathode), followed by measurement of emission luminance (brightness) with time so as to determine a time (luminance half-life) required for decreasing an initial luminance (60-220 cd/m 2 ) to ½ thereof. 
   The results are shown in Table 45 appearing hereinafter. 
   Comparative Example 1 
   A comparative luminescence device was prepared and evaluated in the same manner as in Examples 3-11 except that the Ir complexes (metal coordination compounds shown in Table 45) was changed to Ir-phenylpyridine complex (Ir(ppy) 3 ) shown below. 
                        
 
 
 
   The results are also also shown in Table 45 below. 
                                                     TABLE 45                       Ex. No.   Compound No.   Luminance half-life (Hr)                                        Ex. 3   6   700           Ex. 4   23   850           Ex. 5   43   950           Ex. 6   54   800           Ex. 7   72   850           Ex. 8   99   750           Ex. 9   118   600           Ex. 10   153   700           Ex. 11   440   650           Comp. Ex. 1   Ir (ppy) 3     350                        
 
 
   As is apparent from Table 45, compared with the conventional luminescence device using Ir(ppy) 3 , the luminescence devices using the metal coordination compounds of formula (1) according to the present invention provide longer luminance half-lives, thus resulting in an EL device having a high durability (luminance stability) based on a good stability of the metal coordination compound of formula (1) of the present invention. 
   EXAMPLE 12 
   A color organic EL display apparatus shown in  FIG. 2  was prepared in the following manner. 
   An active matrix substrate had a planar structure basically similar to a structure described in U.S. Pat. No. 6,114,715. 
   Specifically, on a 1.1 mm-thick glass substrate, top gate-type TFTs of polycrystalline silicon were formed in an ordinary manner and thereon, a flattening film was formed with contact holes for electrical connection with a pixel electrode (anode) at respective source regions, thus preparing an active matrix substrate with a TFT circuit. 
   On the active matrix substrate, a 700 nm-thick pixel electrode (anode) of ITO having a large work function was formed in a prescribed pattern. On the ITO electrode, prescribed organic layers and a 100 nm-thick Al electrode (cathode) were successively formed by vacuum deposition with a hard mask, followed by patterning to form a matrix of color pixels (128×128 pixels). 
   The respective organic layers corresponding to three color pixels (red (R) green (G) and blue (B)) were consisting of the following layers. 
   &lt;R Pixel Region&gt; 
   α-NPD (40 nm)/CBP: Ex. Comp. No. 487 (93:7 by weight) (30 nm)/BCP (20 nm)/Alq 3 (40 nm) 
   &lt;G Pixel Region&gt; 
   α-NPD (50 nm)/Alq 3 (50 nm) 
   &lt;B Pixel Region&gt; 
   α-NPD (50 nm)/BCP (20 nm)/Alq 3 (50 nm) 
   When the thus-prepared color organic EL display apparatus was driven, desired color image data can be displayed stably with good image qualities. 
   EXAMPLE 13 
   Synthesis of Ex. Comp. No. 24 
   It is easy to synthesize the following compound in the same manner as in Example 1 except for using 2-chloro-5-trifluoromethylpyridine (made by Tokyo Kasei Kogyo K.K.) instead of 2-bromopyridine in Example 1. 
   Tris[2-(9,9-dimethylfluorene-2-yl)-5-trifluoromethylpyridine-C 3 ,N]iridium (III). 
   EXAMPLE 14 
   Synthesis of Ex. Comp. No. 25 
   It is easy to synthesize the following compound in the same manner as in Example 1 except for using 2-chloro-4,5-bis(trifluoromethyl)pyridine (made by Oakwood Products Inc.) instead of 2-bromopyridine in Example 1. 
   Tris[2-(9,9-dimethylfluorene-2-yl)-4,5-bis(trifluoromethyl)pyridine-C 3 ,N]iridium (III). 
   EXAMPLE 15 
   Synthesis of Ex. Comp. No. 26 
   It is easy to synthesize the following compound in the same manner as in Example 1 except for using 2-chloro-5-methylpyridine (made by Aldrich Co.) instead of 2-bromopyridine in Example 1. 
   Tris[2-(9,9-dimethylfluorene-2-yl)-5-methylpyridine-C 3 ,N]iridium (III). 
   EXAMPLE 16 
   Synthesis of Ex. Comp. No. 28 
   It is easy to synthesize the following compound in the same manner as in Example 1 except that 2-bromo-9,9-diethylfluorene was synthesized from 2-bromofluorene and iodoethane in the same manner as the process described in Example 1 at page 32 of Japanese Laid-Open Patent Application (Tokuhyo Hei) 11-510535 (corr. to U.S. Pat. No. 5,708,130) and was modified ito 2-(9,9-diethylfluorenyl)borate in the same manner as in Example 1 (of the present application), followed by reaction with 2-bromopyridine to synthesize 2-{2-(9,9-diethyl-fluorenyl)pyridine and then reaction with iridium (III) acetylacetonate in the same manner as in Example 1. 
   Tris[2-(9,9-diethylfluorene-2-yl)pyridine-C 3 ,N]iridium (III). 
   EXAMPLE 17 
   Synthesis of Ex. Comp. No. 29 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iodopropane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-propyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 18 
   Synthesis of Ex. Comp. No. 30 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iodobutane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-butyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 19 
   Synthesis of Ex. Comp. No. 31 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iodopentane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-pentyl)fluorene-2-yl]pyridine-C 3  N}iridium (III). 
   EXAMPLE 20 
   Synthesis of Ex. Comp. No. 32 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iodohexane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-hexyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 21 
   Synthesis of Ex. Comp. No. 33 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iodoheptane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-heptyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 22 
   Synthesis of Ex. Comp. No. 34 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iodooctane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-octyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 23 
   Synthesis of Ex. Comp. No. 35 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-iododecane (made by Aldrich Co.) instead of iodoethane and using 2-chloro-5-trifluoromethyl-pyridine (made by Tokyo Kasei Kogyo K.K.) instead of 2-bromopyridine, in Example 16. 
   Tris{2-[9,9-di(1-decyl)fluorene-2-yl]-5-trifluoromethylpyridine-C 3 ,N}iridium (III). 
   EXAMPLE 24 
   Synthesis of Ex. Comp. No. 37 
   It is easy to synthesize the following compound in the same manner as in Example 16 except for using 1-bromoeicosane (made by Aldrich Co.) instead of iodoethane in Example 16. 
   Tris{2-[9,9-di(1-eicosyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 25 
   Synthesis of Ex. Comp. No. 44 
   It is easy to synthesize the following compound in the same manner as in Example 2 except for using 2-(9,9-diethylfluorenyl)boronic acid instead of 2-(9,9-dimethylfluorenyl)boronic acid in Example 2. 
   Tris[2,5-bis(9,9-diethylfluorene-2-yl)pyridine-C 3 ,N]iridium (III). 
   EXAMPLE 26 
   Synthesis of Ex. Comp. No. 45 
   It is easy to synthesize the following compound in the same manner as in Example 2 except for using 2-[9,9-di(1-pentyl)fluorenyl]boronic acid instead of 2-(9,9-dimethylfluorenyl)boronic acid in Example 2. 
   Tris{2,5-bis[9,9-di(1-pentyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 27 
   Synthesis of Ex. Comp. No. 47 
   It is easy to synthesize the following compound in the same manner as in Example 2 except for using 2-[9,9-di(1-pentadecyl)fluorenyl]boronic acid instead of 2-(9,9-dimethylfluorenyl)boronic acid in Example 2. 
   Tris{2,5-bis[9,9-di(1-pentadecyl)fluorene-2-yl]pyridine-C 3 ,N}iridium (III). 
   EXAMPLE 28 
   Synthesis of Ex. Comp. No. 146 
   It is easy to synthesize the following compound in the same manner as in Example 1 except for using dibenzofuran-4-boronic acid (made by Frontier Scientific Inc.) instead of 2-(9,9-dimethylfluorenyl)-boronic acid in Example 1. 
   Tris[2-(dibenzofuran-4-yl)pyridine-C 3 ,N]iridium (III). 
   EXAMPLE 29 
   Synthesis of Ex. Comp. No. 147 
   It is easy to synthesize the following compound in the same manner as in Example 1 except for using dibenzothiophene-4-boronic acid (made by Frontier Scientific Inc.) instead of 2-(9,9-dimethylfluorenyl)boronic acid in Example 1. 
   Tris[2-(-dibenzothiophene-4-yl)pyridine-C 3 ,N]iridium (III). 
   EXAMPLE 30 
   Synthesis of Ex. Comp. No. 149 
   It is easy to synthesize the following compound in the same manner as in Example 2 except for using dibenzofuran-4-boronic acid (made by Frontier Scientific Inc.) instead of 2-(9,9-dimethylfluorenyl)-boronic acid in Example 1. 
   Tris[2,5-bis(dibenzofuran-4-yl)pyridine-C 3 ,N]iridium (III) 
   EXAMPLE 31 
   Synthesis of Ex. Comp. No. 150 
   It is easy to synthesize the following compound in the same manner as in Example 2 except for using dibenzothiophene-4-boronic acid (made by Frontier Scientific Inc.) instead of 2-(9,9-dimethylfluorenyl)-boronic acid in Example 2. 
   Tris[2,5-bis()dibenzothiphene-4-yl)pyridine-C 3 ,N)iridium (III). 
   EXAMPLE 32 
   An organic EL device shown in  FIG. 1C  was prepared in the following manner. 
   On a 100 nm-thick patterned ITO electrode (anode) formed on a 1.1 mm-thick no-alkali glass substrate, a 40 nm-thick charge transport layer of α-NPD was formed by vacuum deposition (10 −4  Pa) at a deposition rate of 0.1 nm/sec. On the charge transport layer, a 40 nm-thick luminescence layer (co-deposited film) of CBP: iridium complex of Ex. Comp. No. 23 (93:7 by weight) was formed by co-vacuum deposition at deposition rates of 0.1 nm/sec (for CBP) and 0.09 nm/sec (for the iridium complex) by controlling heating conditions of deposition vessel. On the luminescence layer, a 40 nm-thick exciton diffusion prevention layer of BCP (Bathocuproine) was formed by vacuum deposition at a deposition rate of 0.1 nm/sec, and or the exciton diffusion prevention layer, a 20 nm-thick electron transport layer of Alq 3 was formed by vacuum deposition at a deposition rate of 0.1 nm/sec. Thereafter, or the electron transport layer, a 150 nm-thick aluminum electrode (cathode) was formed by vacuum deposition at a deposition rate of 1 nm/sec. 
   The thus-prepared organic EL device exhibited an EL spectrum showing λmax=545 nm and luminescent efficiencies of 12.4 lm/W at a luminance of 100 cd/m 2  and 13.6 lm/W at a luminance of 600 cd/m 2 . 
   EXAMPLE 33 
   An organic EL device was prepared and evaluated in the same manner as in Example 32 except for using Tris[2,5-bis(9,9-dimethylfluorene-2-yl)-pyridine-C 3 ,N]iridium (III) (Ex. Comp. No. 43) in place of Tris[2-(9,9-dimethylfluorene-2-yl)pyridine-C 3 ,N]iridium (III) (Ex. Comp. No. 23) synthesized in Example 1. 
   The thus-prepared organic EL device exhibited an EL spectrum showing λmax=590 nm and luminescent efficiencies of 2.4 lm/W at a luminance of 100 cd/m 2  and 1.9 lm/W at a luminance of 300 cd/m 2 . 
   EXAMPLE 34 
   Synthesis of Ex. Comp. No. 54 
   It is easy to synthesize the following compound in the same manner as in Example 1 except for using 4-phenyl-1-bromopyridine (made by General Intermediates of Canada) instead of 2-bromopyridine in Example 1. 
   Tris[2-(9,9-dimethylfluorene-2-yl)-4-phenylpyridine-C 3 ,N]iridium (III). 
   As described above, according to the present invention, the metal coordination compound of the formula (1) characterized by the aromatic group of the formula (5) as a partial structure is an excellent material which exhibits a high emission quantum efficiency. The electroluminescence device (luminescence device) of the present invention using, as a luminescent center material, the metal coordination compound of the formula (1) is an excellent device which not only allows high-efficiency luminescence but also retains a high luminance for a long period and shows little deterioration by current passage. Further, the display apparatus using the electroluminescence device of the present invention exhibits excellent display performances.

Technology Category: 5