三维超分子化合物[Zn(H_2O)_6]·(C_(16)H_8O_8)的合成、晶体结构及荧光光谱

以醋酸锌和3,3’,4,4’-联苯四羧酸(H4BPTC)为原料,采用水热法合成了一个三维超分子化合物Zn(H2O6)].(C16H8O8)(1)。通过红外光谱、元素分析和X射线单晶衍射对其结构进行了表征,X射线单晶衍射分析结果表明,该超分子化合物属于三斜晶系,PT空间群,晶胞参数a=0.654 8(1)nm,b=0.793 9(2)nm,c=0.968 1(2)nm,α=76.29(3)°,β=87.75(3)°,γ=86.43(3)°,Z=1,R1=0.066 5,wR2=0.183 3,GOF=1.021.并通过荧光光谱研究了1在溶液和固态时的发光性能,在室温DMSO溶液中,当激发波长为316nm时,化合物1在399nm处有一强发射峰,呈现蓝紫色荧光,在室温固态时,该化合物的发射峰发生明显红移,在525nm处有一宽谱带发射峰,呈现绿色荧光,这可以归因于在固态化合物1的分子中存在氢键和π—π堆积的相互作用,可以明显降低分子中基态与激发态之间的能量差距,从而使发射峰红移。

Hydrothermal synthesis, crystal structure and luminescence property of 3D supermolecular compound [Zn(H2O)6].(C16H8O8)

A supermolecular compound Zn(H2O)6].(C16H8O8) was synthesized with 3,3', 4,4'-bipthenyltetracarboxylic acid (H4BPTC) and Zn(CH3COO)2.2H2O. Its structure was determined by single crystal X-ray diffraction, IR and element analysis. The crystal belongs to triclinic system with space group and the cell parameters are: a = 0.65484 (13) nm, b = 0.79388 (16) nm, c = 0.96812 (19) nm, alpha = 76.29 (3) degrees, beta = 87.75 (3) degrees, gamma = 86.43 (3) degrees, Z=1, R1 = 0.0665, wR2 = 0.1833, and GOF = 1.021. We have studied the luminescence property of compound 1, The compound 1 has blue-purple luminescence in solutions of DMSO and green luminescence in the solid state at room temperature. In the solid state, the emission frequencies for complex 1 are red-shifted compared with their emission maximum peaks in solutions of DMSO. This red-shift of emission energy from solution to solid is likely to be caused by the intermolecular interaction in the solid state that effectively decreases the energy gap.