Syntheses, crystal structures and luminescent properties of Zn(II)/Cd(II) supramolecular complexes incorporating 4-sulfinobenzoate and its in situ oxidized ligand

Content Provider	Semantic Scholar
Author	Wang, Huang Deng, Zhao‐ Peng Zhao, Hui Yan Gao, Shan
Copyright Year	2012
Abstract	Four new complexes containing d10 metal ions, 4-sulfinobenzoic acid (H2222L) and two types of N-heterocyclic ligands, namely, {[Zn(HL)2(H2O)2]n·2nH2O} (1), {[Cd(HL)2(H2O)2]n·2nH2O} (2), [CdL(2,2′-bipy)(H2O)2]2 (3) and [ZnL(4,4′-bipy)(H2O)3]n (4), have been prepared and characterized by element analysis, IR, TG, PL, and powder and single crystal X-ray diffraction. The adjacent Zn(II)/Cd(II) octahedra in complexes 1 and 2 are bridged by the sulfinate group of the HL−−− monoanion in bis-monodentate mode to form 1-D covalent chains. Two Cd(II) pentagonal bipyramids in complex 3 are bridged by a pair of L2−2− dianions in μ2-η2(carboxyl):η1(sulfinate) mode to generate a dinuclear motif. The Zn(II) octahedra in complex 4 are bridged by the 4,4′-bipy into a 1-D chain, whereas the sulfinate groups of L2−2− dianions act as terminal coordinate groups and arrange along the same side of the chain. The aforementioned four complexes are all extended into 3-D supramolecular networks through extensive hydrogen bonds together with π–π stacking interactions. When the Zn(II)/Cd(II) salts, 4,4′-bipy and H2222L are introduced to hydrothermal reactions, two new complexes of {[Zn(4,4′-bipy)2(H2O)4]n·n(SB)·4nH2O} (5) and {[Cd2(SB)2(4,4′-bipy)4(H2O)3]n·3nH2O} (6) are obtained (H22SB = 4-sulfobenzoic acid), in which the SB2−2− dianion is in situ oxidized from H2222L. Complex 5 is a 3-D host–guest supramolecular network by regarding the SB2−2− dianions as guest counteranions. In contrast, the adjacent Cd(II) cations in complex 6 are bridged by the 4,4′-bipy to generate a 1-D zig-zag chain, in which the SB2−2− dianion acts in chelating mode of carboxylate. The structure analyses of these complexes indicate that the coordination ability obeys the following sequence: sulfinate group > carboxyl group > sulfonate group. Moreover, the solid-state luminescent properties of these complexes are also investigated at room temperature.
Starting Page	3501
Ending Page	3508
Page Count	8
File Format	PDF HTM / HTML
DOI	10.1039/C2CE06584C
Volume Number	14
Alternate Webpage(s)	http://www.rsc.org/suppdata/ce/c2/c2ce06584c/c2ce06584c.pdf
Alternate Webpage(s)	https://doi.org/10.1039/C2CE06584C
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article