Construction of noninterpenetrating and interpenetrating Co(ii) networks with halogenated carboxylate modulated by auxiliary N-donor co-ligands: structural diversity, electrochemical and photocatalytic properties

Shao Yun Hao; Suo Xia Hou; Kristof Van Hecke; Guang Hua Cui

doi:10.1039/c6dt04516b

Construction of noninterpenetrating and interpenetrating Co(ii) networks with halogenated carboxylate modulated by auxiliary N-donor co-ligands: structural diversity, electrochemical and photocatalytic properties

Dalton Trans. 2017 Feb 14;46(6):1951-1964. doi: 10.1039/c6dt04516b.

Authors

Shao Yun Hao¹, Suo Xia Hou¹, Kristof Van Hecke², Guang Hua Cui¹

Affiliations

¹ College of Chemical Engineering, Hebei Key Laboratory for Environment Photocatalytic and Electrocatalytic Materials, North China University of Science and Technology, Tangshan Hebei 063009, P. R. China. tscghua@126.com.
² XStruct, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium.

PMID: 28112312
DOI: 10.1039/c6dt04516b

Abstract

Six Co(ii)-based coordination polymers (CPs) with characteristic frameworks and topologies-namely, [Co(L1)(DCTP)]_n (1), [Co(L2)(DCTP)]_n (2), [Co(L3)(DCTP)]_n (3), {[Co₃(L4)₃(DCTP)₃·H₂O]·H₂O}_n (4), [Co(L5)_1.5(DCTP)]_n (5) and [Co(L6)(DCTP)]_n (6)-were successfully hydrothermally synthesized by employing the halogenated linear ligand 2,5-dichloroterephthalic acid (H₂DCTP). The interpenetrated structures could be rationally modulated by auxiliary N-donor co-ligands containing 1,1'-(1,4-butanediyl)bis-1H-benzimidazole (L1), 1,4-bis(5,6-dimethylbenzimidazol-1-yl)-2-butylene (L2), 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene (L3), 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene (L4), 1,2-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene (L5) and 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene (L6). These diaphanous crystals were clearly characterized by elemental analysis, infrared (IR) spectra and X-ray powder diffraction (XRPD) as well as single-crystal X-ray diffraction analysis. With the aid of the flexible N-donor co-ligands, CP 1 occupies a non-interpenetrated 2D sheet with the point symbol {4⁴·6²} sql net topology, CP 2 possesses a 3D hexagon-shaped network with the point symbol {6⁶} three-fold interpenetrated sqc6 topology, CP 3 exhibits a 2D layer with the point symbol {4⁴·6²} sql net topology, CP 4 reveals an unusual 3D framework with the point symbol {4²·6³·8} three-fold interpenetrated sra topology, CP 5 has a 3D hexagon-shaped network with the point symbol {6⁶} two-fold interpenetrated sqc6 topology, while CP 6 displays a 3D hexagon-shaped network with the point symbol {6⁶} three-fold interpenetrated sqc6 topology. The diverse structures of CPs 1-6 illustrate that the substitute group and position of the methyl group of the bis(benzimidazole) derivatives play a significant role in the assembly of such interpenetrated frameworks. Moreover, luminescence properties and thermal behavior, as well as the electrochemical and photocatalytic properties of CPs 1-6 on the degradation of methylene blue, are also presented.