两个基于双咪唑基配体的Co(Ⅱ)/Cu(Ⅰ)配合物的合成、晶体结构及荧光性质

Syntheses,Crystal Structures and Photoluminescent Properties of Two Co(Ⅱ)/Cu(Ⅰ)Coordination Polymers Based on Bis(imidazol)Ligands

以Co(ClO4)2·6H2O/Cu(ClO4)2·6H2O、1,4-双(咪唑基-1-基)丁烷(bib)/1,4-双(咪唑基-1-基)苯(bix)和4,4-(1,3-苯基双(亚甲基氧基))二苯甲酸(H2pmda)为原料,在水热条件下反应,得到了2个配合物{[Co(bib)3](ClO4)2}n(1)和{[Cu3(bix)(4.5)](ClO4)3}n(2)(H2pmda未参与反应),对它们进行了元素分析、红外光谱、荧光光谱、单晶和粉末X射线衍射表征。配合物1属于三方晶系,R 空间群,a=b=1.39337(5)nm,c=1.74054(13)nm,V=2.9265(3)nm^3,Mr=828.59,Dc=1.410g·cm^-3,F(000)=1293,μ=0.639mm^-1,Z=3,R1=0.0611,wR2=0.1937(I>(2σ(I))。配合物2也属于三方晶系,P 空间群,a=b=2.33441(15)nm,c=0.71511(9)nm,V=3.3749(5)nm^3,Mr=1561.28,Dc=1.536g·cm^-3,F(000)=1602,μ=1.131mm^-1,Z=2,R1=0.0439,wR2=0.1090(I>(2σ(I))。单晶结构分析表明配合物1为含有36元环的二维网状结构,配合物2为含有84元环的二维网状结构,并通过氢键或π-π堆积使它们扩展成超分子结构。此外,还研究了2个配合物的荧光性质。

Two coordination polymers,{[Co(bib)3](ClO4)2}n(1)and{[Cu3(bix)4.5](ClO4)3}n(2),(bib=1,4-bis(imidazol-1-yl)-butane,bix=1,4-bis(imidazol-1-ylmethyl)benzene)have been hydrothermally synthesized by using Co(ClO4)2·6H2O/Cu(ClO4)·6H2O,1,4-bis(imidazolyl-1-yl)butane/1,4-bis(imidazolyl-1-yl)benzene and 4,4'-(1,3-phenylenebis(methyleneoxy))dibenzoic acid(H2pmda)as raw materials and structurally characterized by elemental analysis,IR spectrum,fluorescence spectrum,single-crystal and powder X-ray diffraction.Complex 1 crystallizes in trigonal system,space group R3 with a=b=1.39337(5)nm,c=1.74054(13)nm,V=2.9265(3)nm3,Mr=828.59,Dc=1.410 g·cm^-3,F(000)=1293,μ=0.639 mm-1 and Z=3.The final R1=0.0611 and wR2=0.1937 for 1274 observed reflections with I>2σ(I).Complex 2 belongs to trigonal system too,space group P3 with a=b=2.33441(15)nm,c=0.71511(9)nm,V=3.3749(5)nm3,Mr=1561.28,Dc=1.536 g·cm-3,F(000)=1602,μ=1.131 mm^-1 and Z=2.The final R1=0.0439 and wR2=0.1090 for 3167 observed reflections with I>2σ(I).Structural analyses reveal that complex 1 shows 2D network structure with 36-membered ring and complex 2 possesses 2D network structure with 84-membered ring.The intermolecular hydrogen bonding orπ-πstacking interactions extend the complexes 1 and 2 into supramolecular architectures.Furthermore,we also studied the fluorescence properties of the complexes.