bluuebunny/crossref_metadata_2025_split huggingface dataset:
para‐Functionalized NCN‐Pincer Palladium(II) Complexes: Synthesis, Catalysis and DFT Calculations
Authors: Dijkstra Harm P. , Slagt Martijn Q. , McDonald Aidan , Kruithof Cornelis A. , Kreiter Robert , Mills Allison M. , Lutz Martin , Spek Anthony L. , Klopper Wim , Klink Gerard P. M. van , Koten Gerard van 
Published: February 2003

AbstractSeveral para‐substituted NCN‐pincer palladium(II) complexes (1a−g and 6a−g) {NCN = [C6H3(CH2NMe2)2‐2,6]−, para = 4‐position} have been prepared and the electronic influences of the para substituents were studied in catalysis as well as by DFT calculations (B3LYP/LANL2DZ). From DFT calculations, it was found that the para substituent exerts only a minor effect on the partial charge, investigated by means of the Mulliken population analysis, at the palladium(II) center. Also, when the para‐functionalized, cationic NCN−PdII complexes 6a−g were applied as Lewis acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl α‐cyanoacetate, only small differences in the activities of the various catalysts were observed. These results, when translated to immobilized multipincer catalysts, imply that various para functionalities can be used for immobilization of the pincer−metal complexes without affecting the catalytic activity of the individual sites. The application of a number of shape‐persistent nanosize (NCN−PdII)n complexes (7, n = 3; 8, n = 3; 9, n = 8; 10, n = 12) as homogeneous catalysts in the same Michael reaction, confirmed this expectation. For complexes 7, 8 and 9, the catalytic activity per PdII center was found to be the same as for the monopincer analogs. Only dodecakis(NCN−PdII) complex 10 showed an almost threefold enhancement in catalytic activity per PdII center, which is ascribed to the high catalyst concentration at the periphery of this material. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Investigation of the Ligand Exchange Behavior of Square‐Planar Nickel(II) Complexes by X‐ray Absorption Spectroscopy and X‐ray Diffraction
Authors: Feth Martin P. , Klein Axel , Bertagnolli Helmut 
Published: February 2003

AbstractThe local structure of nickel and bromine in three square‐planar nickel(II) complexes [(2,2′‐bipyridyl)(bromo)(mesityl)nickel(II)] (1), [(bromo)(N,N‐diisopropyl‐1,2‐ethanediimine)(mesityl)nickel(II)] (2), [(bromo)(mesityl)bis(triphenylphosphane)nickel(II) (3)] and their ligand exchange behavior towards several solvents has been determined by means of X‐ray Absorption Near Edge Spectroscopy (XANES), Extended X‐ray Absorption Fine Structure Spectroscopy (EXAFS), X‐ray Diffraction (XRD), multinuclear NMR and UV/Vis spectroscopy. Several square‐planar and octahedral nickel(II) complexes were prepared and spectroscopically characterized as reference compounds. The exchange behavior strongly depends on the nature of the incoming donor ligand (solvent molecule). In some cases the substitution of one or more ligands was accompanied by conservation of the square‐planar geometry. In other solvents the geometry changed from square‐planar to octahedral. The structural information obtained is important to the further development of such nickel(II) complexes as catalysts for various applications. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Regiospecific Cyclometalation of Diphenyl(2‐substituted phenyl)phosphane with Methyltetrakis(trimethylphosphane)cobalt(I)
Authors: Klein Hans‐Friedrich , Beck Robert , Flörke Ulrich , Haupt Hans‐Jürgen 
Published: February 2003

AbstractThe pre‐chelate molecules 2‐(diphenylphosphanyl)‐N,N‐dimethylaniline, [2‐(diphenylphosphanyl)benzyl]dimethylamine, 1‐(diphenylphosphanyl)‐2‐ethylbenzene, 1‐(diphenylphosphanyl)‐2‐isopropylbenzene, and 2‐(diphenylphosphanyl)benzonitrile, in a reaction with [CoMe(PMe3)4], eliminate methane to afford the selectively 6‐ortho‐metalated complexes 1−5 that contain four‐membered metallacycles. The molecular structure of 3 shows a tbp‐coordinated cobalt atom, with axial C and PMe3 donor groups. Metalation in the aliphatic side‐chain occurs with 2‐(diphenylphosphanyl)toluene, giving complex 6 that contains a five‐membered metallacycle. Benzyldiphenylphosphane is selectively ortho‐metalated in the benzyl group, affording 7. As shown by the molecular structures, complex 7 is a true ligand isomer of 6. Substitution of a trimethylphosphane group in compounds 4 and 6 by ethene gives the pentacoordinate complexes 8 and 9, respectively. The ethene ligand is π‐coordinated in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, complex 6 forms monocarbonyl complex 10. Carbonylation of complexes 3 and 4 proceeds by insertion of CO into the Co−C bond under ring expansion, affording the aroylcobalt complexes 11 and 12, respectively. Complex 6 reacts with iodomethane in an oxidative substitution reaction yielding a structurally characterized octahedral complex mer‐13, which eliminates a methyl group in THF at 20 °C to form a pentacoordinate cobalt(II) complex 14. Complex 3 oxidatively adds iodomethane in a stereoselective cis addition to give the cobalt(III) complex mer‐15, which retains its four‐membered metallacycle and the CoCH3 group. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Single‐AtomO‐Bridged Urea in a Dinickel(II) Complex together with NiII4, CuII2and CuII4Complexes of a Pentadentate Phenol‐Containing Schiff Base with (O,N,O,N,O)‐Donor Atoms
Authors: Mukherjee Soumen , Weyhermüller Thomas , Bothe Eberhard , Wieghardt Karl , Chaudhuri Phalguni 
Published: February 2003

AbstractA pentadentate phenol‐containing ligand (H3L) with N2O3donor atoms yields NiII2(1), NiII4(2), CuII2(3) and CuII4(4) complexes, which have been structurally characterized by X‐ray diffraction. Complex1contains a single‐atomO‐bridged urea. The compounds were characterized by IR, UV/Vis, mass spectrometry, electrochemistry and variable‐temperature (2−295 K) magnetic susceptibility measurements. Analysis of the susceptibility data shows antiferromagnetic interactions between the metal centers indicating a diamagnetic ground state for complexes1,3and4, whereas complex2, a tetranuclear NiIIcubane, has a complicated low‐lying magnetic structure with a non‐diamagnetic ground state. A plot ofJvs. Ni−O−Ni angles for all structurally characterized Ni4O4cubane cores, including2, irrespective of their symmetry exhibits a large variation ofJvalues within a small range of Ni−O−Ni angles. The electrochemistry of all complexes was investigated in detail and the ligand‐centered oxidation to a radical‐ligand is inferred from the occurrence of oxidation processes at potentials which are similar. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
(Allenylidene)ruthenium Complexes with Redox‐Active Substituents and Ligands
Authors: Hartmann Stephan , Winter Rainer F. , Brunner Birgit M. , Sarkar Biprajit , Knödler Axel , Hartenbach Ingo 
Published: February 2003

AbstractWe describe the allenylidene complexes [TpL2Ru=C=C=CPhR]+ SbF6− [Tp = HB(pz)3−, L2 = 2 PPh3 or 1,1′‐bis(diphenylphosphanyl)ferrocene (dppf), R = Ph or ferrocenyl] and their spectroscopic and electrochemical characteristics. Three of these compounds possess redox‐active, ferrocene‐based substituents or ligands − that are oxidized at lower potentials than the ruthenium center itself − attached either to the terminal carbon atom of the allenylidene ligand or to the ruthenium atom. The Fc/Ph‐substituted complexes 3a and 3b provide unique examples of hindered rotation of the allenylidene substituent around the M=C bond. For 3a (L2 = 2 PPh3), two isomers differing in the orientation of the vertically aligned, unsymmetrically substituted allenylidene ligand are discernible even at 388 K. The dppf‐substituted congener 3b has the allenylidene ligand in a horizontal orientation and exhibits a rotational barrier, as determined by dynamic 31P NMR spectroscopy, of ΔG≠ = 47 kJ/mol at TC = 238 K. The changes in the spectroscopic and electrochemical properties upon replacement of the PPh3 by a dppf ligand and the Ph by an Fc moiety can be explained in terms of the bonding within these systems. These effects are attenuated when the ferrocene‐based redox tags are oxidized, as shown by IR and UV/Vis spectroelectrochemistry. Thus, infrared spectroelectrochemistry reveals a blue shift of the allenylidene stretch upon oxidation of the dppf ligand, while oxidation of the ferrocene covalently linked to the unsaturated C3 ligand has the opposite effect. Oxidation of the ruthenium atom influences the bonding within the unsaturated ligand more profoundly. Results from IR spectroelectrochemistry point to a vinylidene structure in the RuIII state. Reduction enhances the contribution of alkynyl‐type resonance forms to the overall bonding description, as also shown by IR spectroelectrochemistry. For the ferrocenyl‐substituted allenylidene complexes, oxidation and reduction result in bleaching of the intense optical low‐energy absorption band attributed to a ferrocenyl‐to‐allenylidene charge‐transfer process. The EPR spectra of the paramagnetic reduced forms of these complexes also indicate spin delocalization into the aryl substituents attached to the allenylidene ligand. The complexes Tp(dppf)RuCl and [Tp(dppf)Ru=C=C=CPh2]+ SbF6− were also characterized by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Manganese‐Salen Complexes as Oxygen‐Transfer Agents in Catalytic Epoxidations − A Density Functional Study of Mechanistic Aspects
Authors: Cavallo Luigi , Jacobsen Heiko 
Published: February 2003

AbstractThe mechanism of the Jacobsen−Katsuki epoxidation has been investigated by application of density functional theory; the results of a series of calculations for simplified model systems of different spin states are presented. In the chosen computational approach, the epoxidation of ethylene with a cationic five‐coordinate model catalyst is predicted to occur through a radical intermediate, similarly to the reaction mechanism calculated for the corresponding neutral six‐coordinate species. Although the radical intermediate shows a small energetic preference for the quintet state over the triplet state, the computed reaction profile does not suggest that two‐state reactivity involving spin change plays a major role during the oxygen‐transfer step. Comparative orbital analysis of the cationic and the neutral complexes elucidates the role of a ligand trans to the oxo group. A π‐donor trans to the forming OR− ligand in the radical intermediate causes a relative destabilization of a possible quintet occupation, thus conferring spin rigidity to the six‐coordinate species derived from the neutral catalyst. A reaction pathway resulting in rotational collapse might involve a spin‐crossing process. The ligand framework of the tetra‐chelating N,O ligand in the radical intermediate exhibits a considerable amount of ligand folding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A Dinuclear Iron Complex with Two Cofacial [FeS4] Cores Linked by Covalent Ligand Periphery Clamps and Dissociable Thiolate Bridges
Authors: Sellmann Dieter , Peters Kai P. , Molina Raquel Montón , Heinemann Frank W. 
Published: February 2003

AbstractAs part of a long‐term study of dinuclear iron complexes with sulfur‐rich coordination spheres and cofacial, sterically variable binding sites for molecules relevant to nitrogenase, the complex (AsPh4)2 [{Fe(‘apS4’)}2] (5) was synthesized and completely characterized [‘apS4’4− = 1,3‐bis(2,3‐dimercaptobenzamido)propane(4−)]. Complex 5 contains two cofacial [FeIII(S2C6H4R)2]− units linked by [Fe−S−Fe] thiolate bridges and two peripheral propanediamide ligand backbones that are located on opposite sides of the molecular anion and prevent the complete separation of the two [FeS4] cores of 5 if the Fe−S−Fe bridges dissociate. No marked differences were found in the molecular parameters, spectroscopic, magnetic and electrochemical properties of the [Fe2S8] cores in the anion of 5 and the parent complex [{Fe(S2C6H4)2}2]2−. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Vanadium‐Catalysed Aerobic Cleavage of C−C Bonds in Substituted Cyclohexanones To Afford Carboxylic Acids: Two Model Complexes with Tetrahedral Geometry around Vanadium(V)
Authors: Vennat Maxence , Herson Patrick , Brégeault Jean‐Marie , Shul'pin Georgiy B. 
Published: February 2003

AbstractTwo monosilanol/disilanol derivatives were synthesised by treatment of Ph3SiOH or Ph2Si(OH)2 with [nBu4N]VO3 (3) in ethanol solution. The mononuclear anionic dioxo vanadium(V) species [{Ph3SiO}2VO2]− (4) and the dinuclear complex anion [{Ph2SiO2VO2}2]2− (5) thus obtained are unusual and novel model compounds with ≡Si−O−V(O)2O linkages characterised by single‐crystal X‐ray diffraction. The catalytic activities of these tert‐butylammonium complexes, together with those of the simple vanadium derivatives 3 and 5, of the vanadyl precursors VOSO4·5H2O (1) and [VO(acac)2] (2), and also of “H6[PMo9V3O40]·aq”, were tested for aerobic C−C bond cleavage in 2‐hydroxycyclohexanone and 2‐methylcyclohexanone. Monomeric vanadium species show the same chemistry as the polyoxometalate but with lower yields of acids or keto acids, and so the redox and acid properties of HPA‐n (n = 3, 4) are better tuned. Mechanisms for these oxidation reaction, including electron transfer from a substrate coordinated to vanadium, are proposed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Template Synthesis of Chiral Vicinal Diphosphinites as Their PtII and PdII Complexes
Authors: Bergamini Paola , Bertolasi Valerio , Cattabriga Michela , Ferretti Valeria , Loprieno Urania , Mantovani Nicoletta , Marvelli Lorenza 
Published: February 2003

AbstractThe metal‐templated synthesis of a few examples of vicinal diphenylphosphinites is accomplished when the corresponding vicinal diols react with the diphenylchlorophosphane complexes cis‐[MCl2(PPh2Cl)2] (M = Pt, Pd) in anhydrous THF. This process is proposed as a new synthetic route for PtII and PdII complexes of the new ligands 1,2‐bis(diphenylphosphinito)butane, 2,3‐bis(diphenylphosphinito)butane, and 2,3‐bis(diphenylphosphinito)diisopropyl‐L‐tartrate, containing seven‐membered chelate rings including stereogenic carbons. The new chiral phosphane‐phosphinite (R)‐3‐(diphenylphosphanyl)‐2‐(diphenylphosphinito)propanol has also been obtained as a PtII six‐membered chelate. The X‐ray crystal structure of some of the described complexes and NMR evidence of the possibility of removing the ligands from the metal are reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Di‐ and Trivalent Ytterbium Complexes Containing Linked Amino‐ and Amidocyclopentadienyl Ligands
Authors: Trifonov Alexander T. , Spaniol Thomas P. , Okuda Jun 
Published: February 2003

AbstractReactions of the aminocyclopentadienes (C5Me4H)SiMe2NHR (R = Et, allyl, nPr, tBu) with [YbI2(THF)2] in the presence of two equivalents of potassium 1,2‐diphenylethenide in THF at room temperature gave the diamagnetic half‐sandwich complexes [Yb(η5‐C5Me4SiMe2NHR)Ln(μ‐I)]2 (L = THF, n = 2, L = DME, n = 1). The tert‐butylamido derivative [Yb(η5‐C5Me4SiMe2NHtBu)(THF)2(μ‐I)]2 was characterized by X‐ray structural analysis as a dinuclear complex containing a nonchelating aminocyclopentadienyl ligand. Deprotonation of the aminocyclopentadiene (C5H4tBu)SiMe2NHtBu with two equivalents of potassium 1,2‐diphenylethenide in THF, followed by reaction with [YbI2(THF)2] at 60 °C, gave the trivalent ytterbium ate complex [K(DME)][Yb{(η5:η1‐C5H3tBu‐3)SiMe2NtBu}2]. A single crystal X‐ray diffraction study of this complex shows polymeric chains consisting of trivalent ytterbocene units with two chelating amidocyclopentadienyl ligands coordinated to potassium ions. Metalation of the aminoindene (C9H7)SiMe2NHtBu under the same conditions and treatment with [YbI2(THF)2] in THF at ambient temperature resulted in the formation of the divalent ytterbocene complex [Yb{η5‐(1‐C9H6)SiMe2NHtBu}2(THF)2]. The reaction of ytterbium naphthalenide [Yb(C10H8)(THF)2] with one equivalent of (C9H7)SiMe2NHtBu afforded the bis(indenyl) compound which was isolated as its 2,2′‐bipyridyl adduct [Yb{η5‐(1‐C9H6)SiMe2NHtBu}2(bipy)]. It was shown by single‐crystal structural analysis to exhibit a bent metallocene structure with noncoordinating amino side‐chains. The reaction of (C5Me4H)CH2SiMe2NHtBu, which contains a longer CH2SiMe2 bridge, with [Yb(C10H8)(THF)2] gave the complex [Li0.5][Yb(μ‐η5:η1‐C5Me4CH2SiMe2NtBu)(THF)2(μ‐I)0.5]. Single crystal X‐ray structure analysis revealed the presence of polymeric chains consisting of dinuclear iodo‐bridged [Yb(η5:η1‐C5Me4CH2SiMe2NtBu)] units with a chelating linked amidocyclopentadienyl ligand, intermolecularly bridged by lithium ions. The lithium ions are bonded in an η5‐manner to both units, forming a lithocene structure. When YbCl3 was reacted with Li2[(C5H3tBu‐3)SiMe2NCH2CH2X] (X = NMe2, OMe), heterobimetallic complexes Li[Yb{(η5:η1‐C5H3tBu‐3)SiMe2NCH2CH2X}2] with a helical metallocene structure were isolated. The single crystal structure analysis of one of the three possible diastereomers of Li{Yb[(η5:η1‐C5H3tBu‐3)SiMe2NCH2CH2NMe2]2}, viz. the thermodynamically stable (R,R)/(S,S) epimer was performed. When YbCl3 was reacted with one equivalent of Li2[(C5H3tBu‐3)SiMe2NCH2CH2NMe2] and reduced “in situ” with one equivalent of sodium 1,2‐diphenylethenide in THF, the ytterbium(II) metallocene complex [Li(THF)]2[Yb{(η5‐C5H3tBu‐3)SiMe2NH(CH2CH2NMe2)}2(μ‐Cl)2] was isolated, which exhibits a structure with the two amino functions coordinating to the lithium ions and the chloro ligands bridging both the lithium and ytterbium centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Crystal Structure and Magneto‐Structural Correlation of an Unusual Thiocyanato‐Bridged Nickel(II) Compound, [Ni(μ‐NCS)(dpt)(NCS)]2[Ni(μ‐NCS)(dpt)(NCS)]4 [dpt = bis(3‐aminopropyl)amine]
Authors: Kumar Maji Tapas , Mostafa Golam , Clemente‐Juan Juan M. , Ribas Joan , Lloret Francesc , Okamoto Ken‐ichi , Chaudhuri Nirmalendu Ray 
Published: February 2003

AbstractReaction of Ni(ClO4)2·6H2O with bis(3‐aminopropyl)amine (dpt) and ammonium thiocyanate produces the novel thiocyanato‐bridged nickel(II) compound [Ni(μ‐NCS)(dpt)(NCS)]2[Ni(μ‐NCS)(dpt)(NCS)]4, which has been structurally characterised. The structure determination reveals that there are two different molecules in the crystal lattice; one is dinuclear and other is tetranuclear. Low‐temperature magnetic measurements show that there are ferro‐ as well as antiferromagnetic interactions. The ferromagnetic interaction arises from the dinuclear part and the doubly bridged part of the tetranuclear unit; the antiferromagnetic interaction occurs between singly bridged nickel centres in the tetranuclear unit. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Cover Picture
Authors: Fleischer Holger , Mitzel Norbert W. , Schollmeyer Dieter 
Published: February 2003

AbstractThe cover picture shows yellow crystals and red melt of tellurium(II) dimethanethiolate, Te(SCH3)2, together with its molecular structure in the solid state and the lightinduced deposition of elemental tellurium on glass, from a solution of Te(SCH3)2. In the solid state, Te(SCH3)2 exhibits a cis conformation of the methyl groups with respect to the TeS2 plane, an unprecedented case for nonfunctionalized organotrichalcogenides. For Te(SR)2 (R = Me, Et, iPr, tBu) Te−S bonding and Te···S intermolecular distances are correlated, as are 125Te NMR chemical shifts and the ionization energies of the corresponding thiols. Results are rationalized in terms of σ‐ and π‐type np(S)‐σ*(Te−S) orbital interactions. Details are presented in the article by H. Fleischer et al. on p. 815 ff.
Vinylogue Mono‐ and Bimetallic Cationic Sesquifulvalene and Monohydro Sesquifulvalene Complexes for Second Harmonic Generation
Authors: Meyer‐Friedrichsen Timo , Wong Hans , Prosenc Marc H. , Heck Jürgen 
Published: February 2003

AbstractThe donor‐acceptor complexes with a vinylogue monohydro sesquifulvalene and sesquifulvalene backbone of the type [(η5‐C5H5)Ru{µ‐(η5‐C5H4)C2H2(η6‐C7H7)}ML](PF6)n [n = 0: ML = none (1), Cr(CO)3 (2); n = 1: ML = Ru(η5‐C5H5) (3a), Ru(η5‐C5Me5) (3b)] and [(η5‐C5H5)Ru{µ‐(η5‐C5H4)C2H2(η7‐C7H6)}ML](PF6)n [n = 1: ML = none (4), Cr(CO)3 (5); n = 2: ML = Ru(η5‐C5H5) (6a), Ru(η5‐C5Me5) (6b)], respectively, have been synthesised, and spectroscopically and structurally characterised. A charge‐shift correlation was carried out by means of 1H NMR spectroscopic studies and an increased ground‐state donor‐acceptor interaction in the order 5 < 6b < 4 < 6a was found. The corresponding donor‐acceptor interaction in 3a and 3b varies by an insignificant amount. Hyper‐Rayleigh scattering (HRS) was applied to determine the first hyperpolarisability β of the mono‐ and dicationic complexes 3a−6b. The β values obtained for the cationic sesquifulvalene complexes 4−6b are among the largest ever measured for ruthenocenyl containing complexes due to a strong resonance enhancement: the sesquifulvalene complexes 4−6a, 6b show first hyperpolarisabilities which range between 360 and 700 × 10−30 esu, whereas β for the monohydrosesquifulvalene complexes are considerably lower (75 and 162 × 10−30 esu). For the latter complexes the first hyperpolarisability doubles on going from Ru(η5‐C5Me5) (3b) to Ru(η5‐C5H5) (3a) in the acceptor unit. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Macrocyclic, Dinuclear Zinc(II)‐Directed Self‐Assembly with Pyridine, 2,2′‐Bipyridine and 2‐Methylquinoline: μ2‐OH Bridging Bi‐Macrocyclic Complexes and Hydrogen‐Bond‐Supported Donor‐Acceptor Complexes
Authors: Huang Wei , Gou Shaohua , Qian Huifen , Hu Dahua , Chantrapromma Suchada , Fun Hoong‐Kun , Meng Qingjin 
Published: February 2003

AbstractTwo macrocyclic dinuclear zinc(II) complexes (1a and 1b) have been self‐assembled in the presence of pyridine and 2,2′‐bipyridine, respectively, to form μ2‐OH‐bridged bimacrocycles with a Zn4O4 cavity through coordination bonding. The X‐ray structural analysis reveals that both compounds {2a: [Zn4La2(OH)2]2(ClO4)2; 2b: [Zn4Lb2(OH)2]2(ClO4)2} have an open‐mouthed sandwich‐like structure with π−π interactions between parts of two phenyl rings to strengthen two hydroxyl groups connecting the metal atoms in the same direction of the macrocycle. Furthermore, nonclassical C−H···Cl intermolecular interactions have been observed in the crystal of 2b. In addition, the reaction of 1a with quinoline derivatives has yielded novel hydrogen‐bond‐supported donoracceptor complexes {3a: [Zn2La(H2O)2(C10H9N)2](ClO4)2}. The crystallographic study of the complex containing 2‐methylquinoline indicates that two 2‐methylquinoline molecules are linked to two coordinating water molecules above and below the macrocyclic framework through O−H···N hydrogen bonds. The 2‐methylquinoline plane interacts in a face‐to‐face fashion with the phenyl ring of adjacent macrocyclic frameworks, forming an ordered arrangement where one macrocycle and two 2‐methylquinolines are arrayed alternately with almost the same separation. The interplanar distance mentioned before is ca. 3.6 Å. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Photophysical Properties of Hybrid Metal Complexes Containing both 2,2′‐Bipyridine and 2,2′:6′,2′′‐Terpyridine Units
Authors: Harriman Anthony , Hissler Muriel , Khatyr Abderrahim , Ziessel Raymond 
Published: February 2003

AbstractStepwise cross‐coupling reactions between functionalized metallo synthons and bipyridine‐ or terpyridine‐based building blocks afford novel photoactive, hybrid complexes bearing multiple chromophores that function separately or cooperatively according to the nature of the coordinated metal cations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)