Silver pyroarsonates obtained from Ag(I)-mediated in situ condensation of aryl arsonate ligands under solvothermal conditions.
Silver pyroarsonates obtained from Ag(I)-mediated in situ condensation of aryl arsonate ligands under solvothermal conditions.
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DOI：
10.1021/ic301935g
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发表时间：
2013-02
影响因子：
4.6
通讯作者：
Xiang-Ying Qian;Junling Song;J. Mao
中科院分区：
文献类型：
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作者：
Xiang-Ying Qian;Junling Song;J. Mao
四种新的层状银（I）有机胂酸盐，即[Ag（3）（L（3））（CN）]（1）（H（2）L（3）=（PhAsO（2）H）（2）O），[Ag（3）（L（4））（CN）]（2）（H（2）L（4）=（2-NO（2）-C（6）H（4）-阿索（2）H）（2）O），在溶剂热条件下合成了[Ag（3）（HL（5））（H（2）L（5））]（3）（H（3）L（5）= 3-NO（2）-4-OH-C（6）H（3）-阿索（3）H（2））和[Ag（2）（HL（5））]（4）。在化合物1和2的制备过程中，有机胂酸配体（H（2）L（1）= Ph-AsO（3）H（2）; H（2）L（2）= 2-NO（2）-C（6）H（4）-阿索（3）H（2））发生缩合反应，乙腈分子分解为氰根阴离子。分离出H（2）L（4）配体和化合物1-4的单晶，用X-射线单晶衍射法测定了它们的晶体结构。在1中，基于Ag（I）离子和{L（3）}（2-）阴离子的一维（1D）链进一步通过CN（-）互连成二维（2D）层。在2中，相邻的Ag（I）离子在银（I）有机胂酸盐层内进一步被μ（4）-CN（-）阴离子桥接，具有非常短的Ag···Ag接触。在3中，六核{Ag（6）O（12）}簇通过有机胂配体桥连形成银（I）胂杂化层而相互连接.在4中，右手{Ag（4）O（4）}链通过有机胂配体以及额外的Ag-O-Ag桥进一步互连成新的银（I）胂层。化合物1和2分别显示红色和橙红色发射，这可以被认为是配体-金属电荷转移（LMCT）和金属中心（4d-5s/5 p）跃迁的混合物，这些跃迁受到Ag（I）···Ag（I）相互作用的干扰。在从室温冷却到10 K时，化合物1表现出有趣的温度依赖性发射。
Four new layered silver(I) organoarsonates, namely, [Ag(3)(L(3))(CN)] (1) (H(2)L(3) = (PhAsO(2)H)(2)O), [Ag(3)(L(4))(CN)] (2) (H(2)L(4) = (2-NO(2)-C(6)H(4)-AsO(2)H)(2)O), [Ag(3)(HL(5))(H(2)L(5))] (3) (H(3)L(5) = 3-NO(2)-4-OH-C(6)H(3)-AsO(3)H(2)) and [Ag(2)(HL(5))] (4), were synthesized under solvothermal conditions. During the preparations of 1 and 2, condensation of organoarsonate ligands (H(2)L(1) = Ph-AsO(3)H(2); H(2)L(2) = 2-NO(2)-C(6)H(4)-AsO(3)H(2)) and the decomposition of acetonitrile molecules to cyanide anions occurred. Single crystals of H(2)L(4) ligand and compounds 1-4 were isolated, and their crystal structures have been determined by single crystal X-ray diffraction studies. In 1, the one-dimensional (1D) chains based on Ag(I) ions and {L(3)}(2-) anions are further interconnected by CN(-) into two-dimensional (2D) layers. In 2, adjacent Ag(I) ions within the silver(I) organoarsonate layer are further bridged by μ(4)-CN(-) anions with very short Ag···Ag contacts. In 3, the hexanuclear {Ag(6)O(12)} clusters are interconnected by bridging organoarsonate ligands into a silver(I) arsonate hybrid layer. In 4, the right-handed {Ag(4)O(4)} chains are further interconnected by organoarsonate ligands as well as additional Ag-O-Ag bridges into a novel silver(I) arsonate layer. Compounds 1 and 2 display red and orange-red emissions, respectively, which may be assigned to be an admixture of ligand-to-metal charge transfer (LMCT) and metal-centered (4d-5s/5p) transitions perturbed by Ag(I)···Ag(I) interactions. Upon cooling from room temperature to 10 K, compound 1 exhibits interesting temperature-dependent emissions.