Tripodal imidazole frameworks: Reversible vapour sorption both with and without significant structural changes

Abstract

A series of tripodal imidazole frameworks (TIFs) are reported based on a tripodal, cavity-containing tris(imidazole) derivative. In the case of [Co(3)Cl(6)(1)(2)]·n(solvent) (TIF-1) which possesses a doubly interpenetrated framework structure, the material exhibits rigid, permanent porosity and selectively absorbs CO(2). The non-interpenetrated [Co(1)(2)(H(2)O)(2)]Cl(2)·4H(2)O (TIF-2) also absorbs gases and vapours fully reversibly exhibiting a reversible phase change in the process and considerable conditioning and hysteresis. The very highly hydrated [Co(1)(2)]Cl(2)·22H(2)O (TIF-3) irreversibly dehydrates to the layered structure [Co(1)(2)]Cl(2)·H(2)O (TIF-4). A nickel analogue [Ni(1)(2)]Cl(2)·22H(2)O (TIF-5) closely related to TIF-3 is also reported along with two isostructural, non-porous materials [MCl(2)(1)] (M = Mn, TIF-6; M = Cd, TIF-7) based on d(5) and d(10) Mn(II) and Cd(II). Some of the materials may be prepared by mechanochemical as well as solution based methods. We liken TIF-1 to a gas cylinder, TIF-2 to a sponge and TIF-3 to a fragile soda can that is crushed on emptying to give TIF-4.

Highly Efficient Enrichment of Volatile Iodine by Charged Porous Aromatic Frameworks with Three Sorption Sites

“…[6,7] These materials are chemically and hydrothermally stable;h owever, their limited adsorption capabilities lead to low adsorption of iodine.T herefore, scientists are currently investigating alternative iodine capturing materials that have higher affinity,h igher loading capacity,and lower overall cost. Up to now,several examples of iodine inclusion into inorganic porous materials [8][9][10][11] and metal-organic frameworks (MOFs) [12][13][14][15][16][17][18][19][20][21][22][23][24] are known, with the loading weight ratio varying from 8% to 175 %. By contrast, studies focused on enrichment and detection of iodine by porous organic frameworks (POFs) are rare.…”

Redox-promoted associative assembly of metal–organic materials

“…Milling in the presence of a 1 : 1 mixture of PhMe and H 2 O affords the trinuclear complex 11 , composed of three pentacoordinate Zn( SQ ) 2 units surrounding a central TPVB ligand. (§ §Crystallographic data: compound 3 : Zn 2 SQ 4 Py 2 , (CCDC ), orthorhombic, Pbca , a = 10.8810(16) Å, b = 19.5543(28) Å, c = 29.4419(42) Å, Z = 4, R 1 = 0.083, w R 2 = 0.136 (for 4206 reflections with I ≥ 2 σ I ), R 1 = 0.177, w R 2 = 0.163 (for all reflections), S = 1.056; compound 4 : Zn SQ 2 Py 2 , (CCDC ), monoclinic, P 2 1 / c , a = 10.671(5) Å; b = 19.665(9) Å; c = 17.723(8) Å; β = 97.137(7)°; Z = 4, R 1 = 0.108, w R 2 = 0.137 (for 3107 reflections with I ≥ 2 σ I ), R 1 = 0.108, w R 2 = 0.193 (for all reflections), S = 1.015; compound 5 : Zn SQ 2 NMI , (CCDC ), orthorhombic, Pbca , a = 12.2437(8) Å, b = 18.3841(11) Å, c = 30.3846(19) Å, Z = 8, R 1 = 0.049, w R 2 = 0.093 (for 3668 reflections with I ≥ 2 σ I ), R 1 = 0.120, w R 2 = 0.126 (for all reflections), S = 0.992; compound 6 : Zn SQ 2 NMI 2 , (CCDC ), monoclinic, P 2 1 , a = 10.6541(9) Å, b = 19.7432(17) Å, c = 17.8899(15) Å, β = 99.193(1)°, Z = 4, R 1 = 0.058, w R 2 = 0.137 (for 4265 reflections with I ≥ 2 σ I ), R 1 = 0.108, w R 2 = 0.163 (for all reflections), S = 1.016; compound 7 : Zn SQ 2 Phen , (CCDC ) monoclinic, P 2 1 / c , a = 10.404(3) Å, b = 32.256(8) Å, c = 13.672(3) Å, β = 111.664(4)°, Z = 4, R 1 = 0.081, w R 2 = 0.175 (for 2973 reflections with I ≥ 2 σ I ), R 1 = 0.289, w R 2 = 0.297 (for all reflections), S = 1.066; compound 9 : [Zn( SQ ) 2 ] 2 ( BVPB ), (CCDC ), monoclinic, P 21/ n , a = 12.6164(1) Å, b = 18.4537(2) Å, c = 15.3934(2) Å, β = 103.538(1)°, Z = 4, R 1 = 0.0334, w R 2 = 0.1042 (for 5329 reflections with I ≥ 2 σ I ), R 1 = 0.0428, w R 2 = 0.1152 (for all reflections), S = 0.854; compound 10 : [Zn( SQ ) 2 ]( BVPB )·toluene, (CCDC ), monoclinic, P 2 1 / n , a = 7.6947(9) Å, b = 13.1945(15) Å, c = 27.271(3) Å, β = 95.507(2)°, Z = 2, R 1 = 0.058, w R 2 = 0.117 (for 3753 reflections with I ≥ 2 σ I ), R 1 = 0.132, w R 2 = 0.143 (for all reflections), S = 1.001; compound 11 : [Zn( SQ ) 2 ] 3 ( TVPB )·toluene solvate, (CCDC ) triclinic, P 1, a = 15.4724(16) Å, b = 15.4781(16) Å, c = 28.908(3) Å, α = 78.730(4)°, β = 88.358(4)°, γ = 60.122(3)°, Z = 2, R 1 = 0.1496, w R 2 = 0.3209 (for 15 246 reflections with I ≥ 2 σ I ), R 1 = 0.1811, w R 2 = 0.3344 (for all reflections), S = 1.216.) Crystal structure analysis reveals that the trigonal complexes arrange into a loosely packed structure 74–76 with highly disordered solvent molecules occupying otherwise vacant cavities. According to thermogravimetric analysis, the included solvent is removed by heating at 50 °C under reduced pressure.…”

Metal Organic Nanocapsules as Two-Dimensional Network Building Blocks

“…An acid catalysis of pyrogallol and butanol produced the cyclized macrocycle, PgC 3 . Ligand 15 was synthesized through an S N 2 reaction . All other chemicals were commercially available and used without purification.…”

“…Ligand 15 was synthesized through an S N 2 reaction. 47 All other chemicals were commercially available and used without purification. To synthesize the tethered systems, each component was heated to 150 °C in DMF solution and added sequentially at 1:4:16:7 (PgC 3 :Zn(NO 3 ) 2 :Py:15) or 1:4:16:2 (PgC 3 :Zn(NO 3 ) 2 :Py:17) ratios.…”