Metal-Organic Frameworks with Direct Transition Metal-Sulfonate Interactions and Charge-Assisted Hydrogen Bonds

2009 ◽  
Vol 48 (14) ◽  
pp. 6873-6878 ◽  
Author(s):  
Tori Z. Forbes ◽  
Slavi C. Sevov
IUCrData ◽  
2020 ◽  
Vol 5 (10) ◽  
Author(s):  
Rafael A. Adrian ◽  
Diego R. Hernandez ◽  
Hadi D. Arman

The central copper(II) atom of the title salt, {[Cu(CF3SO3)(CH3CN)2(C12H12N2O2)](CF3SO3)} n or [[Cu(CH3CN)2(diOMe-bpy)(CF3SO3)](CF3SO3)] n where diOMe-bpy is 4,4′-dimethoxy-2,2′-bipyridine, C12H12N2O2, is sixfold coordinated by the N atoms of the chelating bipyridine ligand, the N atoms of two acetonitrile molecules, and two trifluoromethanesulfonate O atoms in a tetragonally distorted octahedral shape. The formation of polymeric chains [Cu(CH3CN)2(diOMe-bpy)(CF3SO3)]+ n leaves voids for the non-coordinating trifluoromethanesulfonate anions that interact with the complex through weak hydrogen bonds. The presence of weakly coordinating ligands like acetonitrile and trifluoromethanesulfonate makes the title compound a convenient starting material for the synthesis of novel metal–organic frameworks.


Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.


2018 ◽  
Vol 20 (24) ◽  
pp. 16770-16776 ◽  
Author(s):  
Siwar Chibani ◽  
Michael Badawi ◽  
Thierry Loiseau ◽  
Christophe Volkringer ◽  
Laurent Cantrel ◽  
...  

The potential use of zeolite and MOF materials for the capture of RuO4 has been investigated for the first time. A hydrated form of HKUST-1 could be a promising sorbent due to its ability to form multiple hydrogen bonds.


2020 ◽  
Vol 76 (6) ◽  
pp. 605-615
Author(s):  
Yong-Jin Zhao ◽  
Jian-Ping Ma ◽  
Jianzhong Fan ◽  
Yan Geng ◽  
Yu-Bin Dong

The tridentate organic ligand 4,4′,4′′-(4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-2,6,10-triyl)tribenzoic acid (H3L) has been synthesized (as the methanol 1.25-solvate, C48H39NO6·1.25CH3OH). As a donor–acceptor motif molecule, H3L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H3L molecules construct a two-dimensional (2D) network, which pack together into three-dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H3L and M(NO3)2 salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena-poly[[triaquacadmium(II)]-μ-10-(4-carboxyphenyl)-4,4′-(4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-2,6-diyl)dibenzoato], [Cd(C48H37NO6)(H2O)3] n , I, and poly[[μ3-4,4′,4′′-(4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-2,6,10-triyl)tribenzoato](μ3-hydroxido)zinc(II)], [Zn2(C48H36NO6)(OH)] n , II, were synthesized. Single-crystal analysis revealed that both MOFs adopt a 3D structure. In I, partly deprotonated HL 2− behaves as a bidentate ligand to link a CdII ion to form a one-dimensional chain. In the solid state of I, the existence of weak interactions, such as O—H...O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I. The deprotonated ligand L 3− in II is utilized as a tridentate building block to bind ZnII ions to construct 3D networks, where unusual Zn4O14 clusters act as connection nodes. As a donor–acceptor molecule, H3L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red-shifted with even higher PLQYs of 79 and 85% for I and II, respectively.


2010 ◽  
Vol 39 (14) ◽  
pp. 3384 ◽  
Author(s):  
Yi Du ◽  
Amber L. Thompson ◽  
Nicola Russell ◽  
Dermot O'Hare

Nanoscale ◽  
2018 ◽  
Vol 10 (20) ◽  
pp. 9634-9641 ◽  
Author(s):  
S. Gonen ◽  
O. Lori ◽  
G. Cohen-Taguri ◽  
L. Elbaz

Four first row transition metal-based metal–organic-frameworks were synthesized in activated carbon, showing high electrocatalytic ORR activity with surprising metal-ion dependence.


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