Structure, luminescence, and adsorption properties of two chiral microporous metal-organic frameworks

Two 3D chiral multifunctional microporous MOFs, Zn3(BTC)2(DMF)3(H2O).(DMF)(H2O) (1) and Cd(4)(BTC)3(DMF)2(H2O)2.6(H2O) (2) (H(3)BTC = 1,3,5-benzenetricarboxylic acid and DMF = N,N'-dimethylformamide), have been synthesized in the presence of organic bases tributylamine (TBA) and triethylamine (TEA), respectively. 1 (C(30)H(38)N(4)O(18)Zn(3)) crystallizes in the tetragonal P4(1)2(1)2 space group (a = 13.6929(19) A, c = 50.664(10) A, V = 9499(3) A(3), and Z = 8). 2 (C33H39N2O28Cd4) crystallizes in the tetragonal P4(3)22 space group (a = 10.3503(4) A, c = 52.557(3) A, V = 5630.4(4) A(3), and Z = 4). X-ray crystallography reveals that 1 consists of a 3D open framework with the (6(3))(4)(6(2).8(2).10(2))(6.(4)8(2))(2) topology, but 2 exhibits a 3D open network with the (4(2).5)(2)(4.(4)5.(10)6.(8)7.(4)8(2)) topology. The solid-state excitation-emission spectra show that the strongest excitation peaks for 1 and 2 are at 341 and 319 nm, and their emission spectra mainly show strong peaks at 410 and 405 nm, respectively. The amounts adsorbed of 1 (2) are 169 mg/g (126 mg/g) for H2O, 137 mg/g (102 mg/g) for C2H5OH, and 133 mg/g (99 mg/g) for CH3OH, which are equivalent to the adsorption of about 62 (34) H2O, 20 (11) C2H5OH, and 28 (16) CH3OH per unit cell, respectively.     

Templated metal-organic frameworks: synthesis, structures, thermal properties and solid-state transformation of two novel calcium-adipate frameworks

Two novel calcium-adipate framework materials have been synthesized hydrothermally. GWMOF-7 ([Ca(C6H8O4)(H2O)2]*(C10H8N2)) and GWMOF-8 ([Ca(C6H8O4)(H2O)2]*(C12H12N2)) both formed three-dimensional structures and were characterized with single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy and elemental analysis. Thermal properties were also studied with thermogravimetric analysis, and show that these structures undergo a solid-state transformation into a denser three-dimensional framework.     

Unprecedented interweaving of single-helical and unequal double-helical chains into chiral metal-organic open frameworks with multiwalled tubular structures

Two novel chiral metal-organic open frameworks with unprecedented multiwalled tubular channels and interweaving of single-helical and unequal double-helical units were reported, which possess novel four-connected 4(2)8(3)10 topology and represent the first examples of functional metal-organic frameworks based on both flexible tripodal and flexible bisdentate ligands.     

Construction of robust open metal-organic frameworks with chiral channels and permanent porosity

Four new metal-organic frameworks (MOFs) containing chiral channels have been synthesized using an achiral, triazine-based trigonal-planar ligand, 4,4',4' '-s-triazine-2,4,6-triyltribenzoate (TATB), and an hourglass secondary building unit (SBU): Zn3(TATB)2(H2O)2.4DMF.6H2O (1); Cd3(TATB)2(H2O)2.7DMA.10H2O (2); [H2N(CH3)2][Zn3(TATB)2(HCOO)].HN(CH3)2.3DMF.3H2O (3); [H2N(CH3)2][Cd3(TATB)2(CH3COO)].HN(CH3)2.3DMA.4H2O (4). MOFs 1 and 2 are isostructural and possess (10,3)-a nets containing large chiral channels of 20.93 and 21.23 A, respectively, but are thermally unstable due to the easy removal of coordinated water molecules on the SBU. Replacement of these water molecules by formate or acetate generated in situ leads to 3 and 4, respectively. Formate or acetate links SBUs to form infinite helical chains bridged by TATB to create three-dimensional anionic networks, in which one of the two oxygen atoms of the formate or acetate is uncoordinated and points into the void of the channels. This novel SBU-stabilization and channel-functionalization strategy may have general implications in the preparation of new MOFs. Thermogravimetric analysis (TGA) shows that solvent-free 3' is thermally stable to 410 degrees C, while TGA studies on samples vapor-diffused with water, methanol, and chloroform show reversible adsorption. MOF 3 also has permanent porosity with a large Langmuir surface area of 1558 m2/g. All complexes exhibit similar strong luminescence with a lambdamax of approximately 423 nm upon excitation at 268.5 nm.     

Syntheses, structures and physical properties of transition metal-organic frameworks assembled from trigonal heterofunctional ligands

Six novel metal-organic frameworks (MOFs), {Mn(bpydb)(bpyHdbH)}(n) (1) {[Co(2)(bpydb)(2)](H(2)O)(0.5)}(n) (2), {[Ni(0.5)(bpydbH)(H(2)O)](DMF)(2)}(n) (3), {[Cu(2)(bpydb)(2)](H(2)O)(0.5)}(n) (4), {Zn(bpyHdb)(2)}(n) (5) and {[Cd(0.5)(bpydb)(0.5)(DMF)](H(2)O)}(n) (6), were successfully synthesized by assembling transition metal salts with trigonal heterofunctional ligand 4,4'-(4,4'-bipyridine-2,6-diyl) dibenzoic acid (bpydbH(2)) under hydrothermal and/or solvothermal conditions. Compound 1 features a rare 4-fold interpenetrating (3,5)-connected framework with hms-type topology. Isostructural compounds 2 and 4, constructed by M(2)(COO)(4) secondary building units, exhibit a robust 3D framework with alb topological type in 2-fold interpenetrating mode. Compound 3 consists of 2D (4,4) networks, which are further assembled into the new topological framework with the symbol (5(3)·6(2)·8)(5(3)·6(3))(2) through O-HO interactions. Compound 5 manifests a novel 4-connected interpenetrating framework, constructed by 2D (4,4) layers and interbedded N-HO interactions. Non-interpenetrating honeycomb networks are observed in compound 6, and further packed into a 3D framework featuring 1D channels. The magnetic susceptibility of compound 2 indicates antiferromagnetic interactions between cobalt ions. The photoluminescent properties of 5 and 6 were investigated in the solid state at room temperature.     

Synthetic strategies for chiral metal-organic frameworks

By direct synthesis route, chiral metal-organic frameworks are synthetized with enantiopure ligands or spontaneous resolution; by indirect method, post-synthetic method and chiral inductionare introduced to construct chiral metal-organic frameworks.     

A family of chiral metal-organic frameworks

Chiral metal–organic frameworks with a three‐dimensional network structure and wide‐open pores (>30 Å) were obtained by using chiral trifunctional linkers and multinuclear zinc clusters. The linkers, H₃ChirBTB‐n, consist of a 4,4′,4′′‐benzene‐1,3,5‐triyltribenzoate (BTB) backbone decorated with chiral oxazolidinone substituents. The size and polarity of these substituents determines the network topology formed under solvothermal synthesis conditions. The resulting chiral MOFs adsorb even large molecules from solution. Moreover, they are highly active Lewis acid catalysts in the Mukaiyama aldol reaction. Due to their chiral functionalization, they show significant levels of enantioselectivity, thereby proving the validity of the modular design concept employed.     

Syntheses, structures and properties of cadmium benzenedicarboxylate metal-organic frameworks

The products isolated from the reaction between Cd(NO3)2 x 4H2O and 1,4-benzenedicarboxylic acid (H2bdc) in DMF are very dependent on the conditions. At 115 degrees C, the reaction gives [Cd(bdc)(DMF)]infinity, which has a three-dimensional network structure, whereas at 95 degrees C, 1 is formed alongside [Cd3(bdc)3(DMF)4]infinity 2, which has a two-dimensional network structure. When the reaction is carried out under pressure, it yields [Cd3(bdc)3(DMF)4]infinity 3, which is a supramolecular isomer of 2. The structure of 3 differs from that of 2 regarding the way the Cd3(O2CR)6 units are interlinked to form layers. When the reaction was carried out in DMF that had undergone partial hydrolysis, the only isolated product was [(NMe2H2)2[Cd(bdc)2] x 2DMF]infinity 4. Compound 4 has a three-dimensional triply-interpenetrated diamondoid structure, with dimethylammonium cations and DMF molecules included within the pores. The reaction between Cd(NO3)2 x 4H2O and H2bdc in DEF gave [Cd(bdc)(DEF)]infinity 5, regardless of the solvent quality. Compound 5 has a three-dimensional network structure. The reaction of Cd(NO3)2 x 4H2O and 1,3-benzenedicarboxylic acid (H2mbdc) in DMF gave [Cd(mbdc)(DMF)]infinity 6 which has a bilayer structure. The thermal properties of the new materials have been investigated, and the coordinated DEF molecules from 5 can be removed on heating to 400 degrees C without any change in the powder X-ray diffraction pattern. The H2 sorption isotherm for the desolvated material shows marked hysteresis between adsorption and desorption, and less adsorption than predicted by simulations. Kinetic data indicate that the hysteresis is not due to mass transfer limitations, and the most likely explanation for this behaviour lies in partial collapse of the framework to an amorphous phase under the conditions of activation.     

Crystal structures and magnetic and ferroelectric properties of chiral layered metal-organic frameworks with dicyanamide as the bridging ligand

Two homochiral 2D-layered frameworks composed of a Cu2O2 core and dicyanamide (dca) linkers, [Cu((R)-hmp*)(dca)]n (1) and [Cu((S)-hmp*)(dca)]n (2) (hmp*=alpha-methyl-2-pyridinemethanol), have been synthesized and structurally characterized. Preliminary investigations suggest that 1 and 2 show possible ferroelectric behaviors. Magnetic studies reveal the existence of strong antiferromagnetic interactions between the CuII centers in both complexes. The results demonstrate that 1 and 2 are multifunctional material candidates combining ferroelectric and antiferromagnetic properties in one molecule.     

基于2,5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质

采用溶剂热法, 以2, 5-二溴对苯二甲酸(H₂L)为配体, 分别与六水合硝酸钕、六水合硝酸钆反应合成了 2种镧系金属有机骨架(MOFs):{[Nd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (1)和{[Gd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (2)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明, 2个配合物均是以稀土离子为金属节点, 与配体相互连接, 形成无限延伸的三维网状结构。     

Ionothermal syntheses, crystal structures and properties of three-dimensional rare earth metal-organic frameworks with 1,4-naphthalenedicarboxylic acid

Twelve isostructural rare earth metal-organic frameworks, namely, [Hmim][RE(2)Cl(1,4-NDC)(3)] (RE = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Y (12), Hmim = 1-hexyl-3-methylimidazolium, 1,4-NDCH(2) = 1,4-naphthalenedicarboxylic acid), have been ionothermally synthesized and structurally characterized. The structures feature three-dimensionally anionic frameworks of [RE(2)Cl(1,4-NDC)(3)](n)(n-) with channels in which the Hmim(+) cations are located. The current results are the first ionothermal synthesis of rare earth metal-organic frameworks based on 1,4-NDCH(2) which possess a previously unknown (4,7)-connected 3-nodal network with the Schl?fli symbol of (3(2)·4(2)·5(2))(3(2)·4(9)·5(2)·6(8))(2)(4(3)·6(3))(2). Luminescent and magnetic properties of some of the title compounds have been studied. Thermogravimetric analyses indicated that all these compounds were thermally stable up to ca. 250 °C.     

Functional porphyrinic metal-organic frameworks: crystal engineering and applications

Metal-organic frameworks (MOFs) are a kind of material which are able to integrate functional groups on their framework backbones. The tunable functionalities let MOFs be applied in various fields of luminescence, gas storage, sensing, magnetics, catalysis and biomedical imaging. Because of their interesting properties of structural robustness, catalysis, charge and energy transformations, using porphyrins and metalloporphyrins as synthons for the fabrication of functional MOFs has attracted considerable interest. Many efficient strategies have been established for the construction of functional porphyrinic MOFs, and some of them present interesting properties for potential applications. This perspective is aimed to summarize recent progress on porphyrinic MOFs, including new synthesis strategies and applications.     

Six new metal-organic frameworks based on polycarboxylate acids and V-shaped imidazole-based synthon: syntheses, crystal structures, and properties

Solvothermal reactions of 4,4'-bis(imidazol-1-yl)diphenyl ether (BIDPE) with deprotonated 5-hydroxy-isophthalic acid (5-OH-H(2)bdc), and benzene-1,3,5-tricarboxylic acid (H(3)btc) in the presence of cadmium(II), zinc(II), cobalt(II), nickel(II), and manganese(II) salts in H(2)O or H(2)O/DMF produced six new complexes, namely, [Cd(BIDPE)(5-OH-bdc)·H(2)O](n) (1), [Co(BIDPE)(5-OH-bdc)·H(2)O](n) (2), [Zn(3)(BIDPE)(3)(5-OH-bdc)(3)·4H(2)O](n) (3), [Ni(BIDPE)(2)(5-OH-bdc)(H(2)O)·3H(2)O](n) (4), {[Mn(2)(BIDPE)(2)(5-OH-bdc)(2)](n) (5), and [Ni(BIDPE)(2)(Hbtc)(H(2)O)](n) (6). These complexes were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1 and 2 reveal the same two-dimensional (2D) sheets with a 32-membered [(Cd/Co)(2)(BIDPE)(2)] metallocyclic ring constructed from BIDPE and 5-OH-H(2)bdc with Cd or Co salts. For compound 3, six identical 2D sheets are polycatenated in parallel to form a rare 2D → 2D framework; it displays ferroelectric behavior with a remnant electric polarization (P(r)) of 0.033 μC/cm(2) and an electric coercive field (E(c)) of 11.15 kV/cm. In compounds 4 and 6, only one carboxyl group coordinated to the Ni atom from 5-OH-H(2)bdc or H(3)btc. Compound 5 exists as binuclear Mn clusters, which are linked by BIDPE and 5-OH-H(2)bdc to generate a 2D sheet and displays weak antiferromagnetic character. In addition, the thermal stabilities and photochemical properties of these new complexes have been studied.     

Construction of open metal-organic frameworks based on predesigned carboxylate isomers: from achiral to chiral nets

The four-connected carboxylate ligand N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (TCPPDA) exists as three stereoisomers: a pair of enantiomers (deltaD2- and lambdaD2-TCPPDA) and a diastereomer (C2h-TCPPDA). TCPPDA was predesigned for the construction of isomeric coordination networks. Reactions of M(NO3)2 (M=Cu, Zn, Co) or Nd(NO)3 with TCPPDA under solvothermal conditions gave rise to five novel porous metal-organic frameworks: [Cu2(D2-tcppda)(H2O)2].2 DMSO.6H2O (1), [Cu2(C2h-tcppda)(H2O)2].2DMSO.6H2O (2), [Co3(D2-Htcppda)2].4DEF.5H2O (3), [Nd2(D2-tcppda)(C2h-tcppda)0.5(DMSO)3]3 DMSO5 H2O (4), and [Zn4O(D2-tcppda)1.5].DMF.H2O (5) (DMSO=dimethyl sulfoxide, DEF=diethylformamide, DMF=dimethylformamide). Complexes 1 and 2 are supramolecular isomers, in which all the ligands adopt pseudotetrahedral (both deltaD2- and lambdaD2-TCPPDA) and rectangular (C2h-TCPPDA) geometries, respectively. Both compounds connect paddlewheel secondary building units (SBUs) to form three-dimensional porous networks possessing PtS and NbO nets, respectively. In 3, all ligands possess pseudotetrahedral (both deltaD2- and lambdaD2-TCPPDA) geometry and link hourglass SBUs to form a three-dimensional porous framework. Compound 4 contains all three stereoisomers (C2-, deltaD2-, and lambdaD2-TCPPDA), thus, has both pseudotetrahedral and rectangular geometries. D2-TCPPDA connects the binuclear neodymium units to generate a two-dimensional layer, further linked by C2h-TCPPDA to create a three-dimensional open framework. In 5, all the ligands possess pseudotetrahedral geometry (D2-TCPPDA), as found in 1 and 3. However, all the TCPPDA ligands in 5 appear as either the deltaD2 or the lambdaD2 form, thus, the whole structure is homochiral. Complex 5 crystallizes in the I4(1)32 space group and the octahedral SBU in 5 is connected by the enantiopure TCPPDA to generate a three-dimensional porous network possessing the corundum Al2O3 net. Complexes 1, 2, and 5 possess permanent porosity, and 4 and 5 exhibit strong luminescence at lambdamax=423 and 424 nm, respectively, upon excitation at 268.5 nm.     

Temperature-controlled chiral and achiral copper tetrazolate metal-organic frameworks: syntheses, structures, and I2 adsorption

Four tetrazole-based three-dimensional (3D) metal-organic frameworks (MOFs), {[Cu(II)(btz)]·0.5H(2)O}(n) (1), [Cu(II)(btz)](n) (1'), {[Cu(II)(btz)]·0.5I(2)}(n) (1'·0.5I(2)), and [Cu(II)Cu(I)(2)(btz)(2)](n) (2) [H(2)btz = 1,5-bis(5-tetrazolo)-3-oxapentane)], have been successfully obtained and characterized by crystallography. Compound 1 features a chiral porous framework. The bulk crystallization of 1 is composed of enantiomers 1a (P4(1)) and 1b (P4(3)), which has been demonstrated by the crystal structure analyses of nine crystals of 1 randomly selected. The Cotton effect displayed in the solid-state circular dichroism spectrum of 1 is therefore attributed to enantiomeric excess rather than enantiopurity. The completely dehydrated phase of 1, that is, 1', can adsorb 0.5 I(2) molecule per formula unit to yield compound 1'·0.5I(2), which has been supported by single-crystal X-ray diffraction, elemental analysis, and thermogravimetric analysis. The locations of I(2) in the pores were unambiguously determined, and the interactions between I(2) molecules and the pore structures were investigated. Compound 2 crystallizes in an achiral C2/c space group. Interestingly, the formations of chiral 1 and achiral 2 significantly depend on the reaction temperature. Between 80 and 140 °C, we got compound 1 as the only product. At 150 °C, both 1 and 2 were in coexistence in the final product. From 160 to 180 °C, only compound 2 was obtained. More interestingly, treatment of the crystals of 1 or the mixture of 1 and 2 obtained at 150 °C in their mother liquor at 170 °C yielded the crystals of 2 in a single phase.     

Synthesis, structures, and properties of two three-dimensional metal-organic frameworks, based on concurrent ligand extension

A tritopic carboxylate ligand, tris(4'-carboxybiphenyl)amine (L-H(3)), has been synthesized and applied in the construction of microporous metal-organic frameworks (MOFs). Two novel metal-organic frameworks (MOFs), {[Zn(2)(L)(OH)]·2DMF·H(2)O}(∞) (1) and {[Cu(L-H)(DMA)]·DMA·2H(2)O}(∞) (2), have been constructed out of L-H(3), Zn(2+), and Cu(2+), respectively. 1 has a 2-fold interpenetrating three-dimensional framework formed by L connectors and the [Zn(2)(CO(2))(3)] secondary building units (SBUs). As for 1, it is worth pointing out that one μ(2)-OH group links two Zn atoms between two neighboring SBUs to produce interesting Zn-O-Zn zigzag chains in the structure. 2 has a two-dimensional grid sheet formed by L-H connectors and the typical paddle-wheel [Cu(2)(CO(2))(4)] SBUs. Two-dimensional (2D) sheets nest with each other, which finally forms a three-dimensional (3D) nested framework. Two MOFs are characterized by infrared (IR) spectroscopy, thermogravimetry, single-crystal and elemental analyses, and powder X-ray diffraction methods. Framework 1' exhibits high permanent porosity (Langmuir surface area = 848 m(2)/g), high thermal stability (up to 450 °C), highly active properties for Friedel-Crafts alkylation reaction, as well as the potential application for the CO(2) gas storage and luminescent material. The catalytic results reveal that 2' is indeed an efficient heterogeneous catalyst for olefin epoxidation reactions.     

Conjugated ligands modulated sandwich structures and luminescence properties of lanthanide metal-organic frameworks

A conjugated ligand, 2-(carboxylic acid)-6-(2-benzimidazolyl) pyridine (Hcbmp), and a series of Lanthanide metal-organic frameworks (MOFs) [Ln(2)(cbmp)(ox)(3)(H(2)O)(2)](2)·2H(3)O(+)·7H(2)O (Ln = Sm (3), Eu (4), and Gd (5), H(2)ox = oxalic acid) have been designed and assembled. To elucidate how the conjugated ligands modulate the structures and luminescence properties, we carried out the structural characterizations and luminescence studies of complexes 3 and 4, and their corresponding oxalate complexes [Ln(ox)(1.5)(H(2)O)(3)]·2H(2)O (Ln = Sm (1) and Eu (2)) were also investigated for comparison. The changes of luminescence behaviors upon dehydration and D(2)O-rehydration processes are presented and discussed in detail. The results indicated that, the cbmp(-) ligands distribute on both sides of the ox(-)-Ln bilayer network to construct a sandwich structure. Moreover, the lowest triplet state of cbmp(-) ligands can match well the energy levels of the Sm(3+) and Eu(3+) cations which allow the preparation of new Ln-MOF materials with enhanced luminescence properties. Meanwhile, the crystallinity of solid states produces more substantial change in the luminescence behaviors than removal or replacement of effective nonradiative relaxers.     

基于2，5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质

采用溶剂热法,以2,5-二溴对苯二甲酸(H₂L)为配体,分别与六水合硝酸钕、六水合硝酸钆反应合成了2种镧系金属有机骨架(MOFs)：{[Nd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (1)和{[Gd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (2)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明,2个配合物均是以稀土离子为金属节点,与配体相互连接,形成无限延伸的三维网状结构。     

Toward templated metal-organic frameworks: synthesis, structures, thermal properties, and luminescence of three novel lanthanide-adipate frameworks

Three novel praseodymium-adipate frameworks were synthesized hydrothermally. GWMOF-3 ([Pr(2)(adipic acid)(3)(H(2)O)(4)].adipic acid.4H(2)O) and GWMOF-6 ([Pr(2)(adipic acid)(3)(H(2)O)(2)].4,4'-dipyridyl) formed three-dimensional structures, whereas GWMOF-4 ([Pr(2)(adipic acid)(3)(H(2)O)(2)].H(2)O) produced a more dense, two-dimensional topology. Single-crystal X-ray and powder diffraction, IR spectroscopy, fluorescence spectroscopy, thermogravimetric analysis, and elemental analysis were employed to characterize all samples. GWMOF-6 represents an innovative step forward in metal-organic framework synthesis where a neutral molecular species not used in the construction of the framework is utilized as a structure-directing agent, or template. Furthermore, this template molecule (4,4'-dipyridyl) is shown to sensitize the fluorescence of lanthanide metal centers in a europium analogue of GWMOF-6.     

Microporous metal-organic frameworks incorporating 1,4-benzeneditetrazolate: syntheses, structures, and hydrogen storage properties

The potential of tetrazolate-based ligands for forming metal-organic frameworks of utility in hydrogen storage is demonstrated with the use of 1,4-benzeneditetrazolate (BDT(2)(-)) to generate a series of robust, microporous materials. Reaction of H(2)BDT with MnCl(2).4H(2)O and Mn(NO(3))(2).4H(2)O in N,N-diethylformamide (DEF) produces the two-dimensional framework solids Mn(3)(BDT)(2)Cl(2)(DEF)(6) (1) and Mn(4)(BDT)(3)(NO(3))(2)(DEF)(6) (2), whereas reactions with hydrated salts of Mn(2+), Cu(2+), and Zn(2+) in a mixture of methanol and DMF afford the porous, three-dimensional framework solids Zn(3)(BDT)(3)(DMF)(4)(H(2)O)(2).3.5CH(3)OH (3), Mn(3)(BDT)(3)(DMF)(4)(H(2)O)(2).3CH(3)OH.2H(2)O.DMF (4), Mn(2)(BDT)Cl(2)(DMF)(2).1.5CH(3)OH.H(2)O (5), and Cu(BDT)(DMF).CH(3)OH.0.25DMF (6). It is shown that the method for desolvating such compounds can dramatically influence the ensuing gas sorption properties. When subjected to a mild evacuation procedure, compounds 3-6 exhibit permanent porosity, with BET surface areas in the range 200-640 m(2)/g. The desolvated forms of 3-5 store between 0.82 and 1.46 wt % H(2) at 77 K and 1 atm, with enthalpies of adsorption in the range 6.0-8.8 kJ/mol, among the highest so far reported for metal-organic frameworks. In addition, the desolvated form of 6 exhibits preferential adsorption of O(2) over H(2) and N(2), showing promise for gas separation and purification applications.