Structural properties of [Cu(ii)₃L₆] cages: bridged polyatomic anion effects on unprecedented efficiency of heterogeneous catechol oxidation

Abstract

Self-assembly of CuX2 (X- = BF4-, ClO4-, PF6-, and SbF6-) with a bidentate ethylmethylbis(3-pyridine)silane ligand (L) in the presence of additional polyatomic anions (X’= SiF62- and PF6-) gives rise to...

Water-reservoir properties dependent on packing modes of [Ni(ii)3L6] cages

“…Cyclohexylmethylbis(3-pyridyl)silane (L 2 ) and ethylmethylbis(3-pyridine)silane (L 3 ) were prepared according to the method reported in the literature. 45,58 1 H NMR spectra were recorded on a Varian Mercury Plus 400 instrument operating at 400 MHz. Infrared spectra were obtained on a Nicolet 380 FT-IR spectrophotometer with samples prepared as KBr pellets.…”

“…The new ligand, (3,3,3-trifluoropropyl)methylbis(3-pyridiyl)silane (L 1 ), was synthesized by reaction of dichloromethyl(trifluoropropyl)silane with 3-bromopyridine according to the procedure available in the literature. 45,58 Self-assembly of NiBr 2 with L 1 , L 2 , and L 3 produced light-blue crystals consisting of Br 2 @[Ni 3 L Interestingly, the halide anions bound to Ni(II) cations were partially and fully dissociated in the self-assembled products of NiCl 2 and NiBr 2 , respectively, with ligands in each solvent. The self-assembly reactions under changes of mole ratio, time, and media produced the same cage products, indicating that the X 2 @M 3 L 6 cage is a thermodynamically stable structure.…”

“…37,38 Thus, a recent trend in coordination-molecular systems has been the emphasis on both efficient construction of useful void volumes and discovery of their practical task-specific applications. 39,40 To date, discrete diverse-coordination systems such as dinuclear, trinuclear, tetranuclear, pentanuclear, hexanuclear, and cuboctahedral cages have been reported, [41][42][43][44][45][46][47][48][49][50][51][52] though the confined-space dependency on the packing modes of unique coordination cages remains unexplored. In this context, [Ni(II) 3 L 6 ] cages via self-assembly of NiX 2 (X À = Br À , Cl À ) with a series of three bidentate ligands were systematically constructed, and their packing-dependent confined spaces were observed in their capacities as reversible water-reservoirs.…”

Insight into systematic formation of hexafluorosilicate during crystallization via self-assembly in a glass vessel

“…1–12 Some anions play a significant role in the construction and behaviors of desirable molecular architectures based on negative charge, size, shape, solvents, and pH. 13–18 In particular, F-containing polyatomic anions such as BF 4 − , PF 6 − , and SbF 6 − have been extensively employed for various purposes such as important chemical phenomena, cage-templates, coordination, and the Hofmeister series; 19–26 however, they are known to be not thermodynamically stable depending on conditions 27,28 relative to the F-free polyatomic anions NO 3 − , ClO 4 − , CH 3 CO 2 − , and SO 4 2− . For instance, the PF 6 − anion could be converted to PF n (OH) 6− n − during the complexation of Pd( ii )-L. 29 Furthermore, BF 4 − is known to be changed to the SiF 6 2− anion via subsequent reaction of dissociated F − with the Si–O moieties of a glass vessel or stoneware.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12] Some anions play a signicant role in the construction and behaviors of desirable molecular architectures based on negative charge, size, shape, solvents, and pH. [13][14][15][16][17][18] In particular, F-containing polyatomic anions such as BF 4 À , PF 6 À , and SbF 6 À have been extensively employed for various purposes such as important chemical phenomena, cage-templates, coordination, and the Hofmeister series; [19][20][21][22][23][24][25][26] however, they are known to be not thermodynamically stable depending on conditions 27,28 relative to the F-free polyatomic anions NO 3 À , ClO 4 À , CH 3 CO 2…”