新型氯桥连一维链结构Cd(Ⅱ)配位聚合物的合成、结构及蓝光性能  

Synthesis,Characterization and Blue-emission of Cd(Ⅱ) Coordination Polymers with μ-Chlorine-Bridging One-dimensional Chain Structures

作　　者：黄尖 刘志刚[1] 范瑞清[1] 董玉伟[1] 张会杰[1] 王雨雷 杨玉林[1] 

机构地区：[1]哈尔滨工业大学化学系 [2]航天学院可调谐激光国防科技重点实验室,哈尔滨150001

出　　处：《高等学校化学学报》2015年第3期411-419,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21171044,21371040);国家重点基础研究发展计划项目(批准号:2013CB632900);哈尔滨工业大学理学创新研究发展培育计划项目(批准号:A201416,B201414);理工医交叉学科基础研究培育计划项目(批准号:HIT.IBRSEMA.201409)资助~~

摘　　要：利用2-乙酰基吡啶（acpy）和2-邻甲基苯胺在甲醇中回流反应得到新型希夫碱配体2-{1-[（2-甲基苯基）亚氨基]-乙基}吡啶）（mpep）,通过溶剂热法将acpy和mpep与氯化镉反应得到2种新型氯桥连一维之字链结构Cd（Ⅱ）配位聚合物{[Cd（mpep）]Cl2}n（配合物1）和{[Cd（acpy）]Cl2}n（配合物2）.利用单晶X射线衍射、核磁共振氢谱、元素分析和红外光谱对配合物1和配合物2进行结构表征.结果表明,配合物1和配合物2均为一维之字链状结构.在配合物1中,Cd与mpep配体中2个氮原子和4个氯原子配位,呈六配位顺式八面体构型,并通过2个Cl原子桥连形成一维之字链状结构.在配合物2中,中心金属Cd（Ⅱ）与acpy中的氮原子、氧原子和4个氯原子配位,也呈六配位顺式八面体构型,进一步通过Cl原子桥连相邻金属形成一维之字链状结构.在3种不同极性的溶剂（CH3OH,CH3CN和CH2Cl2）中,两种配位聚合物均呈现蓝色荧光（390-433 nm）,说明2种配位聚合物具有弱溶剂效应;在固态室温下两种配位聚合物也呈现蓝色荧光,最大发射波长分别为440和473 nm.固态最大发射波长比溶液中红移的原因是分子中存在氢键,降低了基态与激发态之间的能级差.在室温下,配合物1和配合物2在3种溶液和固态中均显示出较长的荧光寿命（19.08-60.20μs）。Two coordination polymers, { [ Cd （ mpep ） ] Cl2}n （ 1, mpep = 2- {1-[（ 2-methylphenyl ） imino I- ethyl } pyridine） and { [Cd （ acpy ） ] Cl2}n （ 2, acpy = 2-acetylpyridine ）, were synthesized under solvothermal condition. The structures of complexes 1 and 2 were characterized by single crystal X-ray diffraction analysis, 1H nuclear magnetic resonance （ 1H NMR） spectrometry, elemental analysis and infrared （IR） spectrometry. The results show that both complexes 1 and 2 have 1 D chain structure. The central cadmium （Ⅱ） atom in complex 1 is coordinated by four chloride ions and two nitrogen atoms from mpep, forming a distorted c/s- octahedron coordination geometry, and the Cd （mpep） ] Cl2 unit builds up a polymeric chain by/x2-chlorine- bridging. The central cadmium （Ⅱ） atom in complex 2 is coordinated by a nitrogen atom and an oxygen atom from acpy and four chloride ions, forming a distorted c/s-octahedron coordination geometry, the Cd （acpy） ] Cl2 unit builds up a polymeric chain by/x2-chlorine-bridging. Additionally, the fluorescent properties of the two complexes were characterized in both solid state and in different polar solvents. The results show that complexes 1 and 2 exhibit blue fluorescence emission（ca. 390-433 nm） in CH3 OH, CH3CN and CH2Cl2, indicating that the coordination polymers have weak solvent effect. The emission spectra of complexes 1 and 2 at 298 K are centered at 440 and 473 nm respectively in solid state. Comparing to the emission spectra in solutions, the emission spectra in solid-state undergo obvious red-shift. The lifetime of complexes 1 and 2 are rela-tively long（ ca. 19.08-60. 20 Ixs） at room temperature.

关 键 词：Cd(Ⅱ)配合物 希夫碱 蓝光性能 荧光寿命 

分 类 号：O613[理学—无机化学]