Three copper(II) complexes connected through tetradentate carboxylate linkers and bidentate N-heterocyclic ligands: From 3-D MOF to 1-D chain

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• 作者：Hong-Yan Lin ; Bao Mu ; Xiu-Li Wang ; ^{wangxiuli@bhu.edu.cn} ; Ai-Xiang Tian
• 关键词：Hydrothermal synthesis ; Copper complex ; N-Heterocyclic ligand ; Crystal structure ; Electrochemical property
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 出版时间：1 April, 2012
• 年：2012
• 卷：702
• 期：Complete
• 页码：36-44
• 全文大小：1880 K

文摘

Three copper coordination polymers [Cu₂(bbtc)(bbi)₂]¡¤3H₂O (1) [bbi?=?1,1-(1,4-butanediyl)bis(imidazole), bbtc?=?3,3?4,4?benzophenonetetracarboxylate], [Cu₃(Hbbtc)₂(3-bpfp)₃(H₂O)₂]¡¤10H₂O (2) [3-bpfp?=?bis(3-pyridylformyl)piperazine], and [Cu(H₂bbtc)(4-bpfp)(H₂O)]¡¤H₂O (3) [4-bpfp?=?bis(4-pyridylformyl)piperazine] have been hydrothermally synthesized by self-assembly of aromatic tetracarboxylate ligand bbtcd [bbtcd?=?3,3?4,4?benzophenonetetracarboxylic acid dianhydride], and bidentate N-heterocyclic ligands bbi, 3-bpfp or 4-bpfp. X-ray diffraction analysis reveals that compound 1 is a novel three-dimensional (3-D) metal-organic framework with a binodal (4,4)-connected {6².8⁴}{6⁴.8²}₂ topology. Compound 2 possesses a two-dimensional (2-D) layered structure, in which a trinodal (3,4,4)-connected network with novel {3.6²}₂{3.6³.7²}₂{3².6².7²} topology can be found. Compound 3 displays a one-dimensional (1-D) ribbon polymer chain based on 4-bpfp ligands and H₂bbtc^2- anions. The adjacent layers for 2 and the adjacent chains for 3 are further linked by hydrogen bonding and ¦Ð-¦Ð stacking interactions to form 3-D supramolecular networks. Importantly, bbtcd with different protonation extent displays three different coordination modes in compounds 1-3: the four carboxyl groups of bbtc^4- anions combine with Cu^II ions by tetra(monodentate) mode in 1, three carboxyl groups of Hbbtc^{3?/sup> anions show tri(monodentate) coordination mode and the fourth carboxyl group is protonated in 2, whereas for 3 only two carboxyl groups H₂bbtc2?/sup> anions adopt bis(monodentate) coordination mode and the other two are protonated. N-heterocyclic ligands play important roles in the construction of title complexes with different dimensionality. In addition, the electrochemical properties of the three copper compounds bulk-modified carbon paste electrodes have been reported.}