A novel supramolecular complex [Cu(fum)(dpphen)2]·CH3OH·H2O constructed from N,N′-bidentate chelate ligand
FU Feng1,2, GAO Zi-wei1,*, FENG Yong2, SHANG Jun-fei2, LI Dong-sheng2, WANG Ji-wu2
(1 Collage of Chemistry and Materials Science, Key Laboratory of Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi′an 710062, Shaanxi, China; 2 Department of Chemistry and Chemical Engineering, Key Laboratory of Chemical Reaction Engineering of Shaanxi Province, Yan′an University, Yan′an 716000, Shaanxi, China)
Abstract:
A novel supramolecular complex, [Cu(fum)(dpphen)2]·CH3OH·H2O (fum=fumarate dianion, dpphen=4,7-diphenyl-1,10-phenanthroline), has been prepared from the reaction of bidentate ligand(dpphen), fumarate with CuCl2, and were characterized by element analysis, IR, thermal analysis and X-ray diffraction technique.The results show that the complex is monoclinic, with space group C2/c, a=4.163 8(4) nm, b=1.323 9(1) nm, c=1.936 0(1) nm, β=117.23(9)°; Z=8 and R=0.032 7.Each Cu(Ⅱ) atom is coordinated by four nitrogen atoms from two different dpphens and two oxygen atoms from fumarate with a distorted octahedron geometry.In the complex, a 1D supramolecular ladder-shaped chain is constructed by C—H…O hydrogen bonds between two mononuclears, furthmore, the chains are assembled by π-π stacking interactions of aryl (dpphen) to furnish a 2D supramolecular layer structure.
KeyWords:
4,7-diphenyl-1,10-phenanthroline;copper(Ⅱ)coordination;π-π stacking interactions;hydrogen bonding interactions;crystal structure基于金属和有机配体间的配位键及超分子作用力[1,2]协同构筑具有光、电、磁、吸附等性质的超分子体系已成为现代化学、材料科学等领域内非常活跃和充满前景的研究热点之一[3,4].为实现这一目标,人们广泛应用了螯合等有机配体,其中邻菲罗啉及其衍生物是常用的配体之一,并在超分子配位化学的发展中起着重要作用[5].邻菲罗啉及其衍生物既是电子给体,又是电子受体,能与多种金属离子形成稳定的配合物,加之邻菲罗啉环间具有潜在的芳环堆积作用,易于搭建各类功能超分子体系,所以人们利用邻菲罗啉及其衍生物作为配体已得到了一系列具有生物活性、光学及催化等性质的一维、二维和三维超分子配合物,但有关其衍生物——4,7-二苯基-1,10-邻菲罗啉构筑超分子配合物的研究报道较少[2,3,5,6].另一方面,多元羧酸因其具有单齿、螯合及桥联等多种灵活的键合方式一直受到化学家们的广泛关注,它们与二齿螯合配体可形成具有重要研究价值的超分子体系[1,7].Dalai等人[8]利用1,10-邻菲罗啉(phen)与铜盐反应合成了一维ZigZag型配位聚合物[Cu(fum)(phen)]·2H2O,并研究了其磁性质,文献[9]以Cd(phen)(NO3)2为前体与反丁烯二酸反应合成了具有特殊荧光性质的二维配位聚合物Cd2(fum)2(phen)2.在上述研究的基础上,我们利用phen的衍生物4,7-二苯基-1,10-邻菲罗啉与反丁烯二酸钠及铜盐反应,借助配位键、氢键及π-π堆积相互作用成功构筑了一种新型超分子配合物[Cu(fum)(dpphen)2]·CH3OH·H2O(fum=反丁烯二酸根,dpphen=4,7-二苯基-1,10-邻菲罗啉),进行了元素分析、红外光谱、热分析等表征,研究了其晶体结构.