多种配位聚合物的合成与表征。由长链刚性 N,N'-双齿配体：1,4-双[（x-吡啶基）乙炔基]苯（x = 3 和 4）形成的线性和锯齿形链，包括通过分子间氢键、互穿梯子状聚索烃以及非互穿方格进行的结构转变。
Synthesis and characterization of diverse coordination polymers. Linear and zigzag chains involving their structural transformation via intermolecular hydrogen-bonded, interpenetrating ladders polycatenane, and noninterpenetrating square grid from long, rigid N,N'-bidentate ligands: 1,4-bis[(x-pyridyl)ethynyl]benzene (x = 3 and 4).
作者信息
Zaman Md Badruz, Udachin Konstantin, Ripmeester John A, Smith Mark D, zur Loye Hans-Conrad
机构信息
Steacie Institute for Molecular Science, National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada.
出版信息
Inorg Chem. 2005 Jul 11;44(14):5047-59. doi: 10.1021/ic050080d.
The long, rigid ligands 1,4-bis[(3-pyridyl)ethynyl]benzene (L1) and 1,4-bis[(4-pyridyl)ethynyl]benzene (L2) were used in the synthesis of 10 new organic-inorganic coordination frameworks, each of them adopting different structural motifs. Synthesis, single-crystal X-ray structure determination, and spectroscopic and thermogravimetric analyses are presented. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] with L1 afforded the following one-dimensional zigzag chain structures: [Cd(C20H12N2)0.5(NO3)(CH3OH)]n (1, monoclinic, C2/c; a = 7.586(1) A, b = 23.222(1) A, c = 13.572(1) A, beta = 92.824(1), Z = 4); [{Cu(C20H12N2)(NO3)2(CH3OH)} x CH3OH]n (2, orthorhombic, P2(1)2(1)2(1); a = 8.589(1) A, b = 15.766(1) A, c = 17.501(1) A, Z = 4); [Co(C20H12N2)2(NO3)2(H2O)2] (5, triclinic, P1; a = 7.493(1) A, b = 8.948(1) A, c = 14.854(1) A, alpha = 100.427(1), beta = 97.324(1), gamma = 110.901(1), Z = 1); [Cu(C20H12N2)(hfac)2]n (4, monoclinic, C2/c, a = 18.828(1) A, b = 14.671(1) A, c = 13.427(1) A, beta = 90.447(1) degrees, Z = 4). Moreover, the minority phase compound formed from Cu(NO3)2 x 3H2O and L1 yielded a metallocyclic chain structure, [Cu(C20H12N2)(NO3)]n (3, triclinic, P; a = 8.728(1) A, b = 10.018(1) A, c = 11.893(1) A, alpha = 109.991(1), beta = 97.109(1), gamma = 115.542(1), Z = 1). In addition to the dinuclear coordination complex 5, all other polymeric structures (1-4) from L1 are composed of interpenetrating 2D and 3D cross-linked zigzag chains via hydrogen-bonding interactions. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] and L2 were dependent on the nature of the metal center and resulted in the formation of four different interpenetrating and noninterpenetrating compounds (6-10): [Co(C20H12N2)1.5(NO3)2]n (6, triclinic, P; a = 14.172(1) A, b = 15.795(1) A, c = 18.072(1) A, alpha = 115.380(1), beta = 101.319(1), gamma = 93.427(2), Z = 4), which consists of T-shaped building blocks assembled into three-dimensional interpenetrating polycatenated ladders; [Cd(C20H12N2)2(NO3)2]n (7, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), which adopts a two-dimensional noninterpenetrating square-grid motif; [Cu(C20H12N2)(hfac)2]n (8, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), composed of three sets of distinct one-dimensional linear chains; [Cu(C20H12N2)(EtOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2EtOH (9, triclinic, P; a = 12.248(2) A, b = 13.711(3) A, c = 18.257(4) A, alpha = 108.078(4) degrees, beta = 97.890(4) degrees, gamma = 103.139(5) degrees, Z = 2) and [Cu(C20H12N2)(MeOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2MeOH (10, triclinic, P; a = 12.136(1) A, b = 13.738(2) A, c = 17.563(3) A, alpha = 107.663(3) degrees, beta = 94.805(4) degrees, gamma = 104.021(4) degrees, Z = 2). Both 9 and 10 stack into infinite interpenetrating ladders through bundles of infinite chains and are described in our preliminary communication.
长链刚性配体1,4 - 双[(3 - 吡啶基)乙炔基]苯（L1）和1,4 - 双[(4 - 吡啶基)乙炔基]苯（L2）被用于合成10种新的有机 - 无机配位框架，它们各自采用不同的结构模式。本文介绍了合成方法、单晶X射线结构测定以及光谱和热重分析。M(NO3)2·xH2O（M = Cd(II)、Cu(II)和Co(II)；x = 3 - 6）与Cu(hfac)2·H2O [hfac = 双(六氟乙酰丙酮)] 与L1的反应得到了以下一维锯齿链结构：[Cd(C20H12N2)0.5(NO3)(CH3OH)]n（1，单斜晶系，C2/c；a = 7.586(1) Å，b = 23.222(1) Å，c = 13.572(1) Å，β = 92.824(1)，Z = 4）；[{Cu(C20H12N2)(NO3)2(CH3OH)}·CH3OH]n（2，正交晶系，P2(1)2(1)2(1)；a = 8.589(1) Å，b = 15.766(1) Å，c = 17.501(1) Å，Z = 4）；[Co(C20H12N2)2(NO3)2(H2O)2]（5，三斜晶系，P1；a = 7.493(1) Å，b = 8.948(1) Å，c = 14.854(1) Å，α = 100.427(1)，β = 97.324(1)，γ = 110.901(1)，Z = 1）；[Cu(C20H12N2)(hfac)·2]n（4，单斜晶系，C2/c，a = 18.828(1) Å，b = 14.671(1) Å，c = 13.427(1) Å，β = 90.447(1)°，Z = 4）。此外，由Cu(NO3)2·3H2O和L1形成的少数相化合物产生了一种金属环链结构 [Cu(C20H12N2)(NO3)]n（3，三斜晶系，P；a = 8.728(1) Å，b = 10.018(1) Å，c = 11.893(1) Å，α = 109.991(1)，β = 97.109(1)，γ = 115.542(1)，Z = 1）。除了双核配位络合物5之外，L1的所有其他聚合物结构（1 - 4）均由通过氢键相互作用的二维和三维交联锯齿链相互贯穿组成。M(NO3)2·xH2O（M = Cd(II)、Cu(II)和Co(II)；x = 3 - 6）与Cu(hfac)2·H2O [hfac = 双(六氟乙酰丙酮)] 与L2的反应取决于金属中心的性质，并导致形成四种不同的相互贯穿和非相互贯穿的化合物（6 - 10）：[Co(C20H12N2)1.5(NO3)2]n（6，三斜晶系，P；a = 14.172(1) Å，b = 15.795(1) Å，c = 18.072(1) Å，α = 115.380(1)，β = 101.319(1)，γ = 93.
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