Patent Application: US-201113269451-A

Abstract:
fluorinated metal - organic frameworks are capable of adsorbing and desorbing hydrocarbons , namely , c6 - c8 hydrocarbon oil components . fmofs can be arranged in a variety of configurations and have internal hollow channels and cavities . in fmofs , hydrogen atoms have been substituted completely or partially with fluorine atoms or fluorinated groups in each linking organic ligand . these fmofs can adsorb c6 - c8 hydrocarbons , up to 500 kg / m 3 as demonstrated for toluene , through a combination of superhydrophobicity and capillary action . no water adsorption was detectable even under extreme conditions including moist air near 100 % relative humidity and immersion in water for multiple weeks , demonstrating far superior water resistance to bpl carbon and zeolites . these materials are stable and can be readily recycled by simple desorption many times . the fmofs have applications in removal or containment of organics , particularly in the fields of oil spill cleanup and hydrocarbon storage .

Description:
generally , the present invention relates to a class of neutral , extended nanotubular porous material called “ fluorinated metal - organic frameworks ” (“ fmofs ”), in which all the organic ligands are perfluorinated or partially fluorinated . the fluoro - lined cylindrical channels of the tubular frameworks possess hydrophobic internal cavities as a result of fluorination of all organic ligands . one embodiment of the present invention pertains to rigid , porous fluorous ( i . e ., perfluorinated ) fmofs with fluoro - lined channels that are capable of gas adsorption and desorption . all hydrogen atoms in the fluorous fmofs have been substituted with fluorine atoms . one possible strategy for achieving these fluorous fmofs uses robust , perfluorinated metal - triazolate clusters as building blocks , which consist of 4 - coordinate tetranuclear clusters [ ag 4 l 6 ] connected by 3 - coordinate ag ( i ) centers . potential candidates for these building blocks include polynuclear silver ( i )- triazolate clusters , which bear unsaturated metal sites or exo - n donor atoms ; thus , they can readily assemble into coordination polymers with id chain , 2d sheet , or 3d framework structures . the mainly organic and hydrophobic character of the perfluorinated inner surface of fmofs offers unprecedented potential for enhancing and fine - tuning the affinity for oil adsorbates in the presence of water or moist air . fmof - 1 was the first example of fmof materials , constructed from silver ( i )- 3 , 5 - bis ( trifluoromethyl - 1 , 2 , 4 - triazolate ( agtz ). fmof - 1 and a polymorph thereof , fmof - 2 , are superhydrophobic and highly efficient for selective adsorption of typical aromatic and aliphatic oil components . this is a significant finding given that the confinement and interaction of water in hydrophobic space represent an important issue in science and technology that has attracted increasing interest in the past decade , including water adsorption in activated carbons and all - silica zeolites , functionalized or coated mesoporous materials , as well as biological channels . fig1 shows the building blocks ( top ) and coordination environment of ag + linkers ( bottom ) of fmof - 1 ( left ) and fmof - 2 ( right ). synthesis of particular embodiments of the fmofs utilizes the perfluorinated ligand 3 , 5 - bis ( trifluoromethyl )- 1 , 2 , 4 - triazole (“ hl ”). hl is synthesized from 2 , 5 - dichloro - 1 , 1 , 1 , 6 , 6 , 6 - hexafluoro - 3 , 4 - diazahexa - 2 , 4 - diene ( abdul - ghani , et al . 1995 ). hl then reacts with silver nitrate in methanol to afford colorless crystals upon evaporation and recrystallization from acetonitrile / toluene . a general synthetic scheme is illustrated in fig2 . synthesis of specific compounds are described in the examples below . these examples and the general synthetic scheme can be used in the synthesis of other fluorinated triazole ligands and related fluorinated metal organic frameworks . for example , r f in fig2 can have longer fluorinated alkyl groups or fluorinated aromatic groups . analysis by x - ray crystallography revealed one embodiment , a neutral fmof with the formula { ag 2 [ ag 4 l 6 ]} n , referred to as fmof - 1 . the crystal structure of fmof - 1 , shown in fig3 , shows extended 3d nanotubular open frameworks consisting of 6 - connected tetranuclear [ ag 4 l 6 ] clusters linked by 3 - coordinate ag ( i ) atoms . the crystal data for fmof - 1 are as follows : c 24 ag 6 f 36 n 18 , fw = 1871 . 64 , tetragonal , i - 42d , a = 13 . 3753 ( 7 ) å , c = 39 . 281 ( 4 ) å , v = 7027 . 2 ( 9 ) å 3 , z = 4 , t = 100 k , d c = 1 . 769 g / cm 3 ; r 1 = 0 . 0473 , wr 2 = 0 . 1420 , gof = 1 . 166 . fig3 shows the structure of fmof - 1 at 100 k . the top figures show 50 % thermal ellipsoidal plots of the building blocks , wherein six exo - n atoms of [ ag 4 l 6 ] coordinate to six 3 - coordinate ag ( i ) centers . the lower figures show space - filling representations of the fluoro - lined 3d channels ( left ) and a view down one channel ( right ). in fmof - 1 , the six triazolate ligands utilize their 1 - and 2 - positioned n - atoms to link four 4 - coordinate ag ( i ) centers ( avg . ag — n = 2 . 20 ( 1 ) å and 2 . 64 ( 1 ) å for equatorial and axial bonds , respectively ) into tetranuclear [ ag 4 l 6 ] clusters ( ag . . . ag = 3 . 470 ( 1 ) å ), which utilize their 4 - positioned n - atoms to connect to one another via 3 - coordinate ag ( i ) centers ( avg . ag — n = 2 . 27 ( 2 ) å ), generating a 3d framework of ( 4 2 . 6 )( 4 4 . 6 2 . 8 8 . 10 ) topology . the framework can be viewed as consisting of open - ended , hollow tubes extending along the direction of both the a - and b - crystallographic axes with a crystallographically - imposed s 4 axis lying at the center of each channel . the cylindrical channels of the tubular framework possess hydrophobic internal cavities , as the cf 3 groups of the perfluorinated ligands point into the channels . a cross - section of each fluoro - lined channel in the space - filling representation also shown in fig3 entails a semi - rectangular shape with 12 × 7 . 3 å dimensions . these fluoro - lined channels account for 40 . 6 % of the unit cell volume as calculated by platon ( spek , 2003 ), which is typical for high - porosity mofs . residual electron densities were too low ( max = 0 . 82 e å − 3 ) to locate possible solvent molecules in the cavities , so it is believed that the best structural refinement entails solvent - free channels . the channels entail hexagonal openings with an ag . . . ag distance of 18 . 7 å for the longest diagonal of the non - planar 32 - membered rings . as shown in fig3 , in the embodiment referred to as fmof - 1 , the silver atoms appear to be well protected under the fluorinated walls , imparting unusual air - and photo - stability despite the notoriety of ag ( i ) species for being light sensitive . indeed , fmof - 1 did not change when subjected to uv illumination in air for over 24 hours . fig4 shows packing diagrams for fmof - 1 crystals at 100 k showing the hexagonal coordination geometry of the non - planar 32 - membered rings . the top figure shows a ball - and - stick representation with cf 3 groups omitted while the bottom figure shows a wireframe representation with all atoms included . the same structure was obtained at room temperature after pretreatment of fmof - 1 to remove any solvent or gas molecules in the channels by heating the crystals at 100 ° c . in vacuum . in addition , the structure of a pretreated single crystal of fmof - 1 was studied at 100 k . fig5 shows a packing diagram for fmof - 1 . n 2 crystals at 100 k . the adsorbed n 2 molecules are shown by a space - filling representation . the resulting structure shows nitrogen molecules adsorbed in the open channels even though the only source of n 2 was the liquid nitrogen from the cryostream used for cooling the exposed crystal on the diffractometer ( i . e ., there was no high pressure of n 2 applied to a sealed sample ). the adsorption of n 2 gas also appeared to occur not only in the large open channels but also in the small cavities . the structure shows 5 . 67 n 2 molecules per repeat unit . fig6 shows a packing diagram for fmof - 1 . toluene crystals at 100 k . the adsorbed toluene molecules are shown by a space - filling representation . as seen in fig6 , crystals of fmof - 1 grown from toluene show a structure in which toluene molecules are adsorbed in the large open channels . a further preferred embodiment of the present invention is referred to as fmof - 2 . the fmof - 2 framework is a polymorphic form of the fmof - 1 framework with the same chemical composition of the metal and ligand but with a different packing arrangement of the 3 - d supramolecular structure . fig7 shows a space - filling representation of the fmof - 2 framework at 100 k while fig8 shows a close - up view of the packing diagram for the solvent - containing structure at 100 k , which contains both open channels and cavities . the toluene molecules are lined in a well - organized facial arrangement with respect to the fluorinated walls of both the large channels and smaller cavities , underscoring the superacidity of these fluoro - lined channels and cavities . an additional preferred embodiment of the present invention is referred to as fmof - 3 . the fmof - 3 framework is a polymorphic form of fmof - 1 and fmof - 2 frameworks but with a 2 - d instead of 3 - d supramolecular structure . fig9 shows the packing diagram for fmof - 3 crystals at 100 k . an additional preferred embodiment of the present invention is referred to as fmof - 4 . the fmof - 4 framework is a polymorphic form of fmof - 1 , fmof - 2 , and fmof - 3 . fig1 shows the packing diagram for fmof - 4 crystals at 100k . the structure of fmof - 4 is similar to fmof - 1 and fmof - 2 in that it is a 3 - d framework while it is similar to fmof - 3 in that it contains only small cavities as opposed to large channels . despite the latter , both fmof - 3 and fmof - 4 are useful for gas adsorption because , as shown in fig5 , gas molecules can indeed adsorb in small cavities . the fmofs exhibit many common properties , including solubility in many organic solvents , high thermal -, air -, and light - stability . the stability is likely imparted by the fluorous protection because of the known strength of the c — f bonds that line the channels and cavities as shown above for preferred fluorous embodiments . all fmof materials can be considered as coated frameworks where the fluorous protection is an inherent part of the structure as opposed to being due to adding an external material . another noteworthy property for fmof materials is their high density ( in the 1 . 6 - 2 . 2 g / ml range for select embodiments ). this is extremely important for gas storage applications because it endows high volumetric capacity . the fmof materials contain open channels or cavities which can accommodate gas molecules at relatively high pressure and / or low temperatures to maximize their storage capacity . the gas molecules can then be released by decreasing the pressure and / or increasing the temperatures . the adsorption / desorption processes are usually reversible and can be fully controlled by pressure , temperature , or both . the quantity of h 2 will be very similar in adsorption and desorption points at similar pressures due to the reversibility of the process . the fmof materials of the current invention are not limited to the ag ( i )- triazolate embodiments shown above . other porous ag ( i )- triazolates , as well as other metal - ligand combinations , are possible . other metal components within the framework material can be used according to the present invention , including metal atoms of the main group , transition metal series , and lanthanide series of the periodic system of the elements . among those metal components , particular examples include li + , na + , k + , rb + , be 2 + , mg 2 + , ca 2 + , sr 2 + , ba 2 + , sc 2 + , y 3 + , ti 4 + , zr 4 + , hf 4 + , v 4 + , v 3 + , v 2 + , nb 3 + , ta 3 + , cr 3 + , mo 3 + , w 3 + , mn 3 + , mn 2 + , re 3 + , re 2 + , fe 3 + , fe 2 + , ru 3 + , ru 2 + , os 3 + , os 2 + , co 3 + , co 2 + , rh 2 + , rh + , ir 2 + , ir + , ni 2 + , pd 2 + , pd 0 , pt 2 + , pt 0 , cu 2 + , cu + , ag + , au + , zn 2 + , cd 2 + , hg 2 + , al 3 + , ga 3 + , in 3 + , tl 3 + , si 2 + , ge 4 + , ge 2 + , sn 4 + , sn 2 + , pb 4 + , pb 2 + , as 5 + , as 3 + , as + , sb 5 + , sb 3 + , sb + , bi 5 + , bi 3 + , bi + , and combinations thereof . the ligands used for construction of the fluorinated mofs are also not limited to fluorinated triazolates . besides triazolates , any ligands with two or more donor atoms and two or more fluorine atoms can be used as bridging ligands for construction of fluorinated mofs . with regard to construction of fmofs , several other fluorinated organic ligands , such as fluorinated carboxylates , fluorinated polypyridines , fluorinated phosphines , fluorinated thiolates , and others , for coordination to various soft and hard metal centers , can also be used . potential applications of the current fmofs are wide - ranging and not limited to h 2 or hydrocarbon storage . other examples include storage or transport of other gases , such as ch 4 , o 2 , n 2 , co , co 2 , no n , and vapors of hazardous organic solvents . these materials include fuel , greenhouse gases , and vapors of environmental pollutants and health hazards . the superior acidity and other structural factors discussed above regarding h 2 storage are also valid for these applications . another example is gas separation , which is facilitated by the anticipated high selectivity of our fluorous materials . the affinity of the fmof materials to these aromatic molecules is clearly illustrated by the toluene structures already discussed , particularly fig9 for fmof - 2 . an additional example is use in catalysis . the superior acidity , stability , open structures , and solubility of the fmof materials are excellent features for use in multiple heterogeneous and homogeneous catalytic processes . the present disclosure demonstrates super - high hydrophobic fmofs exhibiting remarkable air and water stability and high capacity with high affinity to c 6 - c 8 hydrocarbons of oil components . these fmofs can selectively adsorb c 6 - c 8 hydrocarbons in preference to water , through a combination of hydrophobicity and capillary action . results suggest that the fmofs represent a promising class of porous materials that should find practical applications in the removal of organics , particularly in the field of oil spill cleanup and hydrocarbon storage . while available fmofs are stable when exposed to water and air , and can be readily recycled many times , the practicality of their use and mass production considerations will increase upon expansion to include abundant metals such as cu and zn instead of ag . water adsorption isotherms reveal that fmof - 1 is superhydrophobic and significantly superior to bpl carbon and zeolite - 5a ( fig1 ( a )). the water stability of fmof - 1 was examined by water adsorption isotherms ( fig1 ) and by single crystal x - ray diffraction . adsorption and desorption isotherms were obtained via ta instruments q5000 sa and vti - sa high sensitivity thermogravimetric dynamic vapor sorption analyzer which enables sorption analysis of dry powder samples of fmof - 1 under controlled temperature and relative humidity / pressure . the balance has a signal resolution of 0 . 01 μg , and a sensitivity of 0 . 1 μg . these isotherms were measured at 25 ° c . by monitoring the weight change of the sample as a function of relative humidity of water or relative pressure of solvents for a known weight of fmof - 1 (˜ 10 mg ). relative humidity levels were stepped up from 0 % to 98 % with an increment of 10 % each step then step down to 0 %. real time weight , temperature , relative humidity / pressure were recorded . when weight change less than 0 . 01 % for 10 min was observed , the test automatically moved to the next step of rp or rh . zeolite - 5a is hydrophilic , which adsorbs water at very low p / p 0 (& lt ; 0 . 1 ). bpl carbon is highly hydrophobic , whose water adsorption isotherm shows no uptake up to p / p 0 = 0 . 4 followed by a steep rise and the attainment of saturation capacity exceeding 800 kg / m 3 at p / p 0 = 0 . 8 with a hysteresis loop ( type v ). in contrast , fmof - 1 shows negligible water adsorption even at p / p 0 up to 0 . 9 ( fig1 ( a )). these results indicate that the large channels ( 1 . 2 × 0 . 8 nm ) in fmof - 1 are “ closed ” to water , rendering a superhydrophobic behavior . according to the water adsorption behavior , porous materials can be classified as hydrophilic , hydrophobic , or superhydrophobic with adsorption of water at low p / p 0 & lt ; 0 . 1 , moderate p / p 0 & gt ; 0 . 3 , or no detectable adsorption at all ( even near 100 % relative humidity ), respectively . few water adsorption isotherms in mof materials are available , perhaps due to reactivity or lack of stability of common mofs , such as mof - 5 and hkust - 1 , upon water exposure . fmof - 1 represents the first example of a superhydrophobic 3 - d porous crystal with a uniform micro - pore size that is “ closed ” to water ; indeed , even immersing fmof - 1 crystals in water for multiple weeks did not compromise the stability , porosity or crystallinity . the water adsorption behavior of fmof - 1 and its superhydrophobic pore surfaces suggest very weak guest - host interactions between fmof - 1 walls and water as a consequence of the presence of fluorine lining in the channel walls . single crystal x - ray diffraction was carried out using a water soaked single crystal of fmof - 1 . the evacuated single crystal of fmof - 1 was soaked in distilled water for several days before collect data on a bruker smatr apex2 ccd - based x - ray diffractometer . the xrd pattern of water soaked fmof - 1 is identical to that of the water untreated sample , indicating the crystal structure of fmof - 1 hold after water - treatment and no water molecules included in the channel or cage of fmof - 1 ( fig1 - 13 , table 1 - 3 below ). the ir spectra were collected using a nicolet 6700 ft - ir spectrometer equipped with a kbr beamsplitter . the micro well plate accessory has an embedded digs detector , for data collection via transmission . the sample plate itself was made from a rectangle of silicon subdivided into cells by a ptfe mask . the experiment setup and data collection were driven by the array automation add - in to the omnic spectroscopy software . processing via a discriminant analysis using tq analyst within array automation allowed the differences in the spectra to be brought out consistently . the ft - ir spectrum was obtained over a frequency between 350 and 4000 cm − 1 . the spectra ( fig1 ) were collected using 128 scans at 4 cm − 1 resolution . the purple line shows ir trace of the evacuated sample . water treatment condition : the evacuated crystal of fmof - 1 was soaked in distilled water for several days before it was carefully sliced off the outside shell for ir data collection . as shown in fig1 , no o — h stretching was observed for water treated fmof - 1 sample above 3200 cm − 1 . adsorption and desorption isotherms were obtained via ta instruments q5000 sa and vti - sa high sensitivity thermogravimetric dynamic vapor sorption analyzer which enables sorption analysis of dry powder samples of fmof - 1 under controlled temperature and relative humidity / pressure . the balance has a signal resolution of 0 . 01 μg , and a sensitivity of 0 . 1 μg . these isotherms were measured at 25 ° c . by monitoring the weight change of the sample as a function of relative humidity of water or relative pressure of solvents for a known weight of fmof - 1 (˜ 10 mg ). relative humidity levels were stepped up from 0 % to 98 % with an increment of 10 % each step then step down to 0 %. real time weight , temperature , relative humidity / pressure were recorded . when weight change less than 0 . 01 % for 10 min was observed , the test automatically moved to the next step of rp or rh . the high porosity of fmof - 1 allows potential access by a variety of organic vapor molecules , particularly the most common oil components embodied by c 6 - c 8 hydrocarbons . the sorption behavior of n - hexane , cyclohexane , benzene , and toluene at 298 k are shown in fig1 ( b ), featuring typical type - i isotherms . at p / p 0 = 0 . 10 , the adsorption of n - hexane and cyclohexane reach saturation , whereas benzene and toluene reach saturation at p / p 0 = 0 . 20 . the strong uptake at low pressure indicates the presence of strong host - guest interactions through confinement effects for aromatic adsorbates . the amounts adsorbed for n - hexane , cyclohexane , benzene and toluene are 175 , 300 , 250 and 240 kg / m 3 , respectively . the toluene and benzene capacity of fmof - 1 is close to the best performing mof known to date ( mof - 5 ), and superior to other mof materials . the c 6 - c 8 oil components adsorption / desorption isotherms in fmof - 1 are found to be fully reversible , indicating that incoming guests can move freely into and out of the channels . this can be attributed to the smaller dimensions of guest molecules ( 2 . 6 × 6 . 8 , 4 . 3 × 4 . 3 , 3 . 3 × 6 . 6 and 4 . 0 × 6 . 6 a 2 for n - hexane , cyclohexane , benzene and toluene , respectively ) than the cavity size in fmof - 1 ( vide supra : also see fig1 illustrating toluene inclusion ). single crystals of fmof - 1 . 2toluene and fmof - 2 . 4toluene were prepared . crystal structure determination for both compounds were carried out using a bruker smatr apex2 ccd - based x - ray diffractometer equipped with a low temperature device and mo - target x - ray tube ( wavelength = 0 . 71073 å ). measurements were taken at 100 ( 2 ) k . data collection , indexing , and initial cell refinements were carried out using apex2 , frame integration and final cell refinements were done using saint . absorption corrections were applied using the program sadabs ( bruker axs inc ., madison , wis .). in the fmof - 1 , c atoms of the highly disordered toluene molecules were refined isotropically . the rest non - hydrogen atoms in both compounds were refined anisotropically . hydrogen atoms in the solvent molecules of the compounds were placed in idealized positions and were refined as riding atoms . structure solution , refinement , graphic and generation of publication materials were performed by using shelxtl software ( bruker analytical x - ray , madison , wis .). refinement details , structural parameters , bond lengths and angles are given in tables 4 - 9 below . for the fmof - 1 . 2toluene structure , toluene molecules were found disordered in two positions and refined accordingly with distance constraints . the occupancy factors of the two solvent molecules were close to 0 . 25 from initial structure refinement . these values were fixed to 0 . 25 in the final structure refinement to give the formula ag 2 [ ag 4 ( tz ) 6 ]. 2toluene for fmof - 1 . 2toluene . in the fmof - 2 . 4toluene , toluene molecules were disordered in two positions with occupancy factors close to 0 . 50 from initial structure parameters and were refined with constrained distances . the toluene adsorption level in fmof - 1 amounts to 8 molecules per unit cell ( 7478 . 4 ( 6 ) å 3 at 298 k ) according to fig1 ( b )&# 39 ; s data , indicative of commensurate adsorption . fig1 shows the isolation of the toluene solvate of fmof - 1 , ag 2 [ ag 4 tz 6 ]. 2toluene , whose crystal structure reveals an adsorption limit of 8 molecules per unit cell , or 1 / 3 toluene solvent molecule per agtz unit . the toluene content based on the crystal structure is in remarkable agreement with the adsorption isotherm . toluene molecules are disordered in two symmetric positions ( highlighted as yellow and blue sphere in fig1 ( a )), and adopt a zig - zag packing within fmof - 1 channels ( fig1 ( b )). fig1 shows a plot of atoms in the asymmetric unit of ag 2 [ ag 4 ( tz ) 6 ]. 2toluene ( fmof - 1 . 2toluene ). the small cages around the main channels in fmof - 1 are large enough to accommodate gas molecules such as n 2 , o 2 and h 2 , with one molecule per cage , but are too small to include oil components like toluene and hexanes enlarging the cage size around the channels , therefore , boosts the oil capacity of such superhydrophobic frameworks . phase transition via annealing is a good strategy to obtain new thermally stable porous crystals . such a framework , [ ag ( ag 3 tz 4 )] 3 / 2 . 4toluene ( fmof - 2 . 4toluene ; fig1 ), has been isolated by annealing fmof - 1 at ca . 300 ° c . overnight and then re - assembling the framework from toluene / acetonitrile , effectively doubling the toluene solvate contents per agtz unit . fmof - 2 is one of several crystal polymorphs of fmof - 1 that have been isolated . the structure of fmof - 2 consists of binuclear [ ag 2 tz 2 ] units ( fig1 ( a )) that are interconnected via sharing the four - coordinate ag ( 1 ) and three - coordinate ag ( 2 ) atoms to form 2d grid sheets ( porous layers ) parallel to the ab plane . the adjacent [ ag 2 tz 2 ] units are crystallographically independent and perpendicular to each other , and are parallel and perpendicular to the c - axis , respectively . these layers are then interconnected vertically via two - coordinate ag ( 3 ) atoms ( ag ( 3 )— n ( 6 ), 2 . 118 ( 8 ) å ) along the c - axis to form a 3 - d porous network with two types of voids along the c - axis : microporous hexagonal channels about 1 . 8 nm in width and triangular - shaped nano - cages with pores about 1 . 0 nm in diameter surrounding the channels ( fig1 ( b )). the defining features of the cages are their two gate openings exposed to adjacent cages along the c - axis , each consisting of three flexible cf 3 groups that provide communication between the cages . both the large channels and small cages are filled by toluene molecules , with 3 and 6 molecules per cage and channel in each layer , respectively . toluene molecules whose planes are parallel to the c - axis are arranged as propeller blades around the c - axis to give a c 3 - and c 6 - symmetrical propeller structure in the cage and channel , respectively . the capacity of toluene in fmof - 2 is doubled compared to fmof - 1 , giving rise to an adsorption limit of 12 toluene molecules per unit cell of 5799 . 8 å 3 . this corresponds to an adsorption density of ˜ 500 kg / m 3 , which represents the highest adsorption density of an oil component reported for any porous material , including activated carbon , zeolites and mofs , known to date . fig1 shows a plot of crystal packing in [ ag ( ag 3 tz 4 )] 3 / 2 . 4toluene ( fmof - 2 . 4toluene ) showing the hexagonal fluorine - lined channel along c - axis . fig1 shows a plot of toluene packing in fmof - 2 . 4toluene showing the propeller arrangement of toluene molecules in the cage ( pale blue ) and in the hexagonal channel ( yellow ). the thermal stability of fmof - 1 and its toluene solvate was examined by tga and single crystal x - ray diffraction . under an air atmosphere , tga of toluene soaked fmof - 1 ( fig2 ) reveals a weight loss of 13 % from 30 to 125 ° c ., corresponding to 8 toluene molecules per unit cell , consistent with the toluene vapor adsorption data shown in fig1 b in the main manuscript . there is no further weight loss from 125 to 300 ° c . ( fig2 ). upon further heating , the obvious weight loss above 310 ° c . corresponds to the sublimation and decomposition of fmof - 1 . at 400 ° c ., the overall weight loss of 85 % for fmof - 1 indicates partial evaporation and decomposition . the guest molecules in fmof - 1 can be easily removed by heating at 100 ° c . under vacuum for 1 h , which can be verified by tga on the desolvated fmof - 1 . the fully desolvated fmof - 1 exhibits no obvious weight loss from 30 to 300 ° c . ( fig2 ). trifluoroacetic acid ( 7 . 6 ml , 0 . 1 mol ) was added to a stirred solution of trifluoroacethydrazide ( 12 . 8 g , 0 . 1 mol ) in benzene ( 100 ml ) and the mixture was heated under reflux for 2 h . a dean and stark trap was fitted , and reflux was continued for 3 h . reflux was continued in the absence of the dean and stark trap ( 3 h ) and then with the trap refitted ( 20 h ). the resulting white solid was collected by filtration , dried in vacuum and identified as 1 , 2 - bis ( trifluoroacetyl ) hydrazine ( 16 . 5 g , 73 %). m . p . 173 - 175 ° c . a mixture of n , n - diethylaniline hydrochloride ( 18 . 5 g , 0 . 1 mol ), 1 , 2 - bis ( trifluoroacetyl ) hydrazine ( 10 . 3 g , 0 . 46 mol ) and phosphoryl chloride ( 160 ml ) was stirred for 30 minutes under nitrogen in a flask fitted with a condenser leading to a cold trap (− 78 ° c .). the mixture was heated under reflux for 5 h and then allowed to cool and stored overnight . the flask contents and the small amount of material which had condensed in the cold trap were combined and the two layers which had formed were separated . the layer was added to ice water ( 85 ml ) and the mixture vigorously stirred for 1 h in a flask fitted with a condenser . separation of the lower organic layer gave the main batch of the crude product ( 6 . 4 g ). the original dark upper layer was treated similarly with ice water ( 75 ml ) and the organic layer subjected to preliminary purification by trap - to - trap distillation in vacuum to afford a second batch of crude product ( 1 . 6 g ). distillation of the combined product through a vacuum - jacketed vigreux column gave 2 , 5 - dichloro - 1 , 1 , 1 , 6 , 6 , 6 - hexafluoro - 3 , 4 - diazahexa - 2 , 4 - diene ( 6 . 3 g , 53 %) as an oil . a solution containing aqueous ammonia ( 0 . 78 g . 45 . 9 mmol ) in diethyl ether ( 30 ml ) was added slowly over 1 h to a stirred solution of 2 , 5 - dichloro - 1 , 1 , 1 , 6 , 6 , 6 - hexafluoro - 3 , 4 - diazahexa - 2 , 4 - diene ( 6 . 0 g , 23 . 0 mmol ) in diethyl ether ( 60 ml ) and water ( 30 ml ) at 0 ° c ., and stirring was continued for 3 h . the ether layer was separated , dried over na 2 so 4 and the ether removed in vacuo to give ( zz )- 1 - amino - 5 - chloro - 1 , 1 , 1 , 6 , 6 , 6 - hexafluoro - 3 , 4 - diazahexa - 2 , 4 - diene . yield : 3 . 6 g ( 64 %). a solution of ( zz )- 1 - amino - 5 - chloro - 1 , 1 , 1 , 6 , 6 , 6 - hexafluoro - 3 , 4 - diazahexa - 2 , 4 - diene ( 5 . 0 g , 20 . 7 mmol ) in thf ( 20 ml ) was heated under reflux for 3 days and the solvent was removed under reduced pressure to give a waxy solid . purification by column ( eluant : chcl 3 ) affords 3 , 5 - bis ( trifluoromethyl )- 1h - 1 , 2 , 4 - triazole as a colorless crystal . yield : 1 . 0 g , 25 %. m . p . 74 - 75 ° c . sodium hydride ( 0 . 24 g , 0 . 01 mol ) was added to 10 ml of anhydrous acetonitrile contained in a three - necked flask fitted with a nitrogen inlet , a dropping funnel and a condenser surmounted with a drying tube ( cacl 2 ). an equivalent amount of 3 , 5 - bis ( trifluoromethyl )- 1h - 1 , 2 , 4 - triazole ( 2 . 0 g , 0 . 01 mmol ) in 5 . 0 ml of anhydrous acetonitrile was added from the dropping funnel and the mixture stirred at room temperature for 24 h under a nitrogen atmosphere . solvent was then removed in vacuo and the white residue of the sodium triazolide was used in the following reaction without separation . agclo 4 . h 2 o ( 225 mg , 1 . 0 mmol ) and the above sodium triazolide ( 250 mg , 1 . 1 mmol ) in 30 ml of meoh was stirred for 6 h and finally concentrated under reduced pressure to a small volume . water was added to the residue and the precipitated colorless solid was filtered , washed with water and dried at 60 ° c . in vacuum to afford colorless crystalline solid . recrystallization from acetonitrile - toluene afford colorless crystals of fmof - 1 , yield : 153 mg ( 49 %). the procedures above can be generally used in the synthesis of other flourinated triazole ligands and related fluorous metal organic frameworks . for example , the r f in fig2 can be replaced by longer flourinated alkyl groups or flourinated aromatic groups instead of cf 3 . abdul - ghani , m . m . ; 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