Composite cluster-organic frameworks based on polyoxometalates and copper/cobalt–oxygen clusters

Abstract

The first two cluster organic frameworks based on Anderson-type polyoxometalates and copper/cobalt-oxo cluster secondary building units have been successfully made under solvothermal conditions.

Syntheses, structures and optical properties of two B3O7 cluster-based borates

“…We speculate that the additional weight loss is assigned to the absorbed water molecules (1.25 H 2 O) in the channels that cannot be mapped by single-crystal X-ray diffraction, which is commonly found in high-symmetry structures or porous frameworks. 2,16,47,48 These water molecules are further stabilized by H-bonds from the BO(OH) 2 groups, making them removable at the common dehydrating temperature. The slightly higher dehydrating temperature of the absorbed water molecules and OH groups on extra framework anions like B(OH) 4 − , HCO 3 − and HCOO − is probably because of their strong H-bond interactions.…”

All-Inorganic Bis-Sb3O3-Functionalized A-Type Anderson–Evans Polyoxometalate for Visible-Light-Driven Hydrogen Production

“…In addition to these high-nuclearity Mo-POMs, there is another well-documented classic Anderson–Evans Mo-POM with a general formula of [H y (XO 6 )­Mo 6 O 18 ] n − ( y = 0–6, n = 2–8, X = Co, Ni, Cr, Cu, Al, etc. ), which can also act as SBBs to form high-nuclearity giant Mo-POMs, organic ligand-modified derivatives, and POM-based MOFs . To date, many organic–inorganic hybrid derivatives of Anderson–Evans Mo-POMs have been reported and are synthesized by covalently tris-functionalizing with organic tris-R ligands (tris = C­(CH 2 OH) 3 , R = NH 2 , NO 2 , CH 3 , etc) .…”

Synthesis, structure and highly selective C3H8/CH4 and C2H6/CH4 adsorption of a (4,8)-c ternary flu-metal–organic framework based upon both [Sc4O2(COO)8] and [Cu4OCl6] clusters

“…40 Very interestingly, the [M 4 O 2 (COO) x S y ] (M = Cu 2+ , Sc 3+ ; S = solvent; x = 4 or 6; y = 2 or 4) clusters are found to be able to serve as the potential cubic 8-connected nodes and the Cu 4 OCl 6 cluster may act as the alternative tetrahedral 4-connected node, although they are rarely encountered in the construction of MOFs. 41–45…”

“…40 Very interestingly, the [M 4 O 2 IJCOO) x S y ] (M = Cu 2+ , Sc 3+ ; S = solvent; x = 4 or 6; y = 2 or 4) clusters are found to be able to serve as the potential cubic 8-connected nodes and the Cu 4 OCl 6 cluster may act as the alternative tetrahedral 4-connected node, although they are rarely encountered in the construction of MOFs. [41][42][43][44][45] Our group has great interest in the construction of MOFs based upon ligands containing N-heterocyclic and carboxyl groups and their environmental and energy related gas adsorption and separation properties. 1,[46][47][48][49][50][51][52][53] Herein, based upon the high-valence Sc 3+ ion being susceptible to coordination with the carboxyl group and the low-valence Cu 2+ ion being subject to coordination with the N-heteroatom, 36,37 The solvothermal reaction of ScCl 3 •6H 2 O and Cu(NO 3 ) 2 •3H 2 O with isonicotinic acid in the solution of N,N′dimethylformamide and acetonitrile at 120 °C successfully afforded a high yield of SNNU-Bai69 as yellow block crystals, which crystalize in the triclinic space group P1 ¯.…”