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首页> 外文期刊>Crystal growth & design >Self-assembly of discrete metallocycle versus coordination polymer based on silver(I) and di-2-and di-3-pyridines with flexible spacer
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Self-assembly of discrete metallocycle versus coordination polymer based on silver(I) and di-2-and di-3-pyridines with flexible spacer

机译:基于银(I)和带有柔性间隔基的二-2-和二-3-吡啶的离散金属环与配位聚合物的自组装

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摘要

Four flexible bis(pyridyl) ligands, namely, 1,3-bis(2-pyridylaminomethyl)benzene (M), 1,3-bis(3-pyridylaminomethyl)benzene (U), 1,4-bis(3-pyridylaminomethyl)benzene (U), and 1,4-bis(2-pyridylaminomethyl)benzene (L4), have been synthesized, and the reactions of these ligands with AgX salts (X = NO3-, ClO4-) lead to the formation of six new complexes, [Ag(L1)](2)(ClO4)(2) (1), (Ag(L2)ClO4](n) (2), [Ag(L3)NO3](n) (3), [Ag(L3)(PPh3)(2)](n)(NO3)(n) center dot nCH(3)OH (4), [Ag-2(L4)(PPh3)(2)(NO3)(2)](n) center dot nH(2)O (5), and [Ag(L4)NO3], (6), exhibiting from zero-dimensional (0-D) to three-dimensional (3-D) frameworks. In complex 1, the L1 ligand bridges two silver atoms to form a dinuclear with a 24-membered macrometallacyclic ring, while the L1 ligand coordinates to silver atoms to generate a 2-D (4,4) network with two pyridine rings oriented in a divergent fashion (or trans conformation) in complex 3. With a similar trans conformation, L2 in complex 2, L3 in complex 4, and L4 in complex 5 connect the adjacent silver atoms or Ag2O2 units which formed by the bridging of nitrate anions in a eta(2):mu(2) fashion to give rise to infinite helical chains, respectively. Complex 6 exhibits a 3-D framework with diamond topology, which is combined by two kinds of helical chains: one is a -Ag-NO3-Ag-NO3- chain with the nitrate anions in a eta(1):eta(1):mu(2) fashion, and another is a -Ag-L4-Ag-L4- chain with the L4 ligand in trans conformation. All of these complexes are photoluminescent in the solid state with spectra that closely resemble those of the ligand precursor.
机译:四个灵活的双(吡啶基)配体,即1,3-双(2-吡啶基氨基甲基)苯(M),1,3-双(3-吡啶基氨基甲基)苯(U),1,4-双(3-吡啶基氨基甲基)已经合成了苯(U)和1,4-双(2-吡啶基氨基甲基)苯(L4),这些配体与AgX盐(X = NO3-,ClO4-)的反应导致形成了六个新的络合物,[Ag(L1)](2)(ClO4)(2)(1),(Ag(L2)ClO4](n)(2),[Ag(L3)NO3](n)(3),[ Ag(L3)(PPh3)(2)](n)(NO3)(n)中心点nCH(3)OH(4),[Ag-2(L4)(PPh3)(2)(NO3)(2) ](n)中心点nH(2)O(5)和[Ag(L4)NO3],(6),显示从零维(0-D)到三维(3-D)框架。配合物1,L1配体桥接两个银原子以形成具有24元大金属环的双核,而L1配体与银原子配位以生成2-D(4,4)网络,其中两个吡啶环以发散性取向复杂3中的时尚形式(或反式构象)。类似的反式构型中,复合物2中的L2,复合物4中的L3和com中的L4络合物5以eta(2):mu(2)的方式连接硝酸根阴离子桥接而形成的相邻银原子或Ag2O2单元,分别产生无限的螺旋链。配合物6展示具有菱形拓扑结构的3-D框架,该框架由两种螺旋链组合而成:一种是-Ag-NO3-Ag-NO3-链,其硝酸根阴离子在eta(1):eta(1)中:mu(2)形式,另一个是带有反式构型的L4配体的-Ag-L4-Ag-L4-链。所有这些配合物都是固态的光致发光体,其光谱与配体前体的光谱极为相似。

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