Huo Yu, Yang Lu, Niu Jingyang, Wang Jingping
Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475001, PR China.
Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475001, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2014 Oct 15;131:484-9. doi: 10.1016/j.saa.2014.04.063. Epub 2014 May 2.
An organic-inorganic hybrid polyoxomolybdate with formula as [Cu(2,2'-bpy)(H2O)]2[Cu(2,2'-bpy)(H2O)3][(O3PCCH3(OH)PO3)2Mo(VI)4O11(H2O)2]·7H2O (1) (2,2'-bpy=2,2'-bipyridine) has been successfully synthesized constructing by diphosphonate H2O3PC(CH3)(OH)PO3H2 (1-hydroxyethylidene-1,1-bisphosphonic acid, noted as HEDP or etidronate) under conventional aqueous solution. 1 was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X-ray photoelectron spectroscopy (XPS). Each anion cluster of 1 can be regarded as the fusion of two {Cu(2,2'-bpy)(H2O)}(O3PCCH3(OH)PO3)Mo(VI)2O6 subunits with an additional six-coordinated Cu(2,2'-bpy) coordination cation linking on one side and there exist weak π-π interactions among the bipyridine groups. The XPS spectra indicate that the oxidation states of Mo and Cu in 1 are +6 and +2, respectively. Photoluminescence properties of 1 and the free 2,2'-bipyridine ligand have been both analyzed, showing that the presence of ligand-to-metal-charge-transfer (LMCT) transitions and metal-ligand coordination have an important effecting on the photoluminescence.
一种分子式为[Cu(2,2'-bpy)(H₂O)]₂[Cu(2,2'-bpy)(H₂O)₃][(O₃PCCH₃(OH)PO₃)₂Mo(VI)₄O₁₁(H₂O)₂]·7H₂O (1)（2,2'-bpy = 2,2'-联吡啶）的有机-无机杂化多金属氧酸盐已通过在传统水溶液中由二膦酸H₂O₃PC(CH₃)(OH)PO₃H₂（1-羟基亚乙基-1,1-二膦酸，记为HEDP或依替膦酸）成功合成。通过单晶X射线衍射、元素分析、红外光谱、热重（TG）分析和X射线光电子能谱（XPS）对1进行了表征。1的每个阴离子簇可视为两个{Cu(2,2'-bpy)(H₂O)}(O₃PCCH₃(OH)PO₃)Mo(VI)₂O₆亚基的融合，在一侧连接有一个额外的六配位Cu(2,2'-bpy)配位阳离子，并且联吡啶基团之间存在弱π-π相互作用。XPS光谱表明1中Mo和Cu的氧化态分别为 +6和 +2。对1和游离的2,2'-联吡啶配体的光致发光性质都进行了分析，结果表明配体到金属电荷转移（LMCT）跃迁和金属-配体配位的存在对光致发光有重要影响。
