An ion-pair compound, [HL]2[Ni(CN)4]4H2O 1 has been obtained as an unexpected product when we attempt to prepare a heterometallic cyano-bridged complex by the reaction of GdCl3nH2O, K2Ni(CN)4 and L (L=4-(2-hydroxyphen...An ion-pair compound, [HL]2[Ni(CN)4]4H2O 1 has been obtained as an unexpected product when we attempt to prepare a heterometallic cyano-bridged complex by the reaction of GdCl3nH2O, K2Ni(CN)4 and L (L=4-(2-hydroxyphenyl)-1,5,9-triazacyclododecan-2-one) in aqueous solution, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.380(1), b = 9.9637(8), c = 17.087(1) ? ?= 105.947(2)? V = 2026.6(3) ?, Rint = 0.0509, Z = 2, Dc = 1.297 g/cm3, C34H56O8N10Ni, Mr = 791.60, F(000) = 844, m(MoKa) = 0.538 mm1, S = 1.030, the final R = 0.0644 and wR = 0.1299 for 2023 observed reflections with I ≥ 2(I). The title compound 1 contains one anion of [Ni(CN)4]2, two cations of [HL]+ and four packing water molecules, which are held together by the NH···O and OH···O hydrogen bonds to form a three- dimensional framework.展开更多
基金National Natural Science Foundation of China(81001669)National Natural Science Foundation of Shaanxi Province(2016JM8028)+1 种基金The Chinese Medicine Project of Shaanxi Province(ZYMS005)Basic and New Medicine Research Key Laboratory Foundation of Shaanxi Provi
文摘以1,4,7-三氮杂环癸烷和氯甲基苯并咪唑为起始原料,一步反应合成了一种新的N-功能化的四齿配体,并用X射线衍射法测定了其铜(Ⅱ)配合物([CuC lL]·[ClO 4])的晶体结构。结果表明,该配合物由阳离子单元[CuC lL]+和阴离子单元ClO-4组成,中心铜原子与一个氯离子、大环配体的三个氮原子和苯并咪唑基的一个氮原子配位,形成扭曲的四方锥结构。为了揭示配合物的配位性质与电子结构之间的关系,基于密度泛函理论,利用DFT-B3LYP/6-31G(d)研究了配合物的前沿分子轨道分布(HOMO,LUMO),Mulliken原子电荷和能带。计算结果表明,2-甲基苯并咪唑基侧基的N(4)原子比N(5)原子具有更强的电荷转移能力,因为N(4)的HOMO和LUMO组分比N(5)的大,证明了Cu和N(4)之间形成了配位键。此外,配合物的前线分子轨道能分别为-0. 18722 a. u.(HOMO)和-0. 10239 a. u.(LUMO)。配合物的能级差ΔE(ELUMO-EHOMO)值为0. 08483 a. u.,较小,说明其在光照条件下容易激发,不稳定。
文摘An ion-pair compound, [HL]2[Ni(CN)4]4H2O 1 has been obtained as an unexpected product when we attempt to prepare a heterometallic cyano-bridged complex by the reaction of GdCl3nH2O, K2Ni(CN)4 and L (L=4-(2-hydroxyphenyl)-1,5,9-triazacyclododecan-2-one) in aqueous solution, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.380(1), b = 9.9637(8), c = 17.087(1) ? ?= 105.947(2)? V = 2026.6(3) ?, Rint = 0.0509, Z = 2, Dc = 1.297 g/cm3, C34H56O8N10Ni, Mr = 791.60, F(000) = 844, m(MoKa) = 0.538 mm1, S = 1.030, the final R = 0.0644 and wR = 0.1299 for 2023 observed reflections with I ≥ 2(I). The title compound 1 contains one anion of [Ni(CN)4]2, two cations of [HL]+ and four packing water molecules, which are held together by the NH···O and OH···O hydrogen bonds to form a three- dimensional framework.
基金Project supported by the National Natural Science Foundation of China （No. 20271041） and S haanxi Natural Science Foundation （No. 2002B04）.Acknowledgments We are grateful for Prof. Wen Zhenyi, who supplied the Gaussian 03 software for us. We also thank Prof. Ng Seik Weng at University of Malaya for the solution of the crystal structure of complex 1.
