基于阴离子调控策略的Co(Ⅱ)配位聚合物的合成、晶体结构及荧光性质
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摘要
以三键桥联吡啶类配体2,6-二(3′-吡啶乙炔基)-4-甲基苯胺(L)为配体,在常温混合溶剂(二氯甲烷-甲醇)中分别与CoCl_2、Co(SCN)2通过自组装反应,获得了一维及二维配位聚合物[Co(L)Cl_2]_n(1)及[Co(L)_2(SCN)_2]_n(2),通过红外、元素分析、X射线单晶衍射等检测手段对所合成的配合物进行了结构表征。对比1和2的单晶结构可以发现,配体L在配位聚合物1和2中的配位取向及结构相似,不同的是Co(Ⅱ)离子的配位数受配位阴离子的影响而不同:配位聚合物1中四配位的Co(Ⅱ)通过2个配体的相互连接呈现一维的弯曲链状结构,而配位聚合物2中六配位的Co(Ⅱ)则通过4个配体的相互连接得到二维的平面结构。2个配合物中均存在氢键及π-π相互作用。通过粉末衍射证明了配位聚合物1和2为单一晶相,其固态下的荧光测试显示,二者的荧光均减弱,并相对于配体L有红移(1)及蓝移(2)。
Two coordination polymers [Co(L)Cl_2]_n(1) and [Co(L)_2(SCN)_2]_n(2) were obtained by using 4-methyl-2,6-bis(pyridin-3-ylethynyl) aniline(L) and Co(Ⅱ) salts in CH_2Cl_2/MeOH mixed solvent under room temperature. The complexes 1 and 2 were characterized by IR, elemental analysis and X-ray single crystal diffraction. The structural analysis revealed that complex 1 has 1D chain structure and 2 has 2D plane structure. The reason of the structure difference was anion choice because the L in both of the coordination complexes adopts almost same trans-N,N donor configuration. Complex 1 has four-coordinated Co (Ⅱ) which coordinated to two L molecules,while complex 2 has six-coordinated Co (Ⅱ) which coordinated to four L molecules. The XRD and fluorescence property of two complexes were investigated. Compared to the emission spectrum of L, the emission maximum of the complex 1 was red shift and 2 was blue shift.
Two coordination polymers [Co(L)Cl_2]_n(1) and [Co(L)_2(SCN)_2]_n(2) were obtained by using 4-methyl-2,6-bis(pyridin-3-ylethynyl) aniline(L) and Co(Ⅱ) salts in CH_2Cl_2/MeOH mixed solvent under room temperature. The complexes 1 and 2 were characterized by IR, elemental analysis and X-ray single crystal diffraction. The structural analysis revealed that complex 1 has 1D chain structure and 2 has 2D plane structure. The reason of the structure difference was anion choice because the L in both of the coordination complexes adopts almost same trans-N,N donor configuration. Complex 1 has four-coordinated Co (Ⅱ) which coordinated to two L molecules,while complex 2 has six-coordinated Co (Ⅱ) which coordinated to four L molecules. The XRD and fluorescence property of two complexes were investigated. Compared to the emission spectrum of L, the emission maximum of the complex 1 was red shift and 2 was blue shift.
引文
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