配位聚合物{[Co_2(HBTC)_2(H_2O)_6]·C_4H_(10)N_2·2H_2O}_n的水热合成、结构表征及荧光性质  

Hydrothermal Synthesis, Structural Characterization and Fluorescent Property of Coordination Polymer {[Co_2(HBTC)_2(H_2O)_6]·C_4H_(10)N_2·2H_2O}_n

作　　者：陈建新 刘世雄[1] 

机构地区：[1]福州大学中心实验室

出　　处：《高等学校化学学报》2004年第7期1189-1193,MJ01,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 1710 12 );福建省自然科学基金 (批准号 :E0 110 0 10 )资助

摘　　要：采用水热法合成了配位聚合物 {[Co2 ( HBTC) 2 ( H2 O) 6 ]· C4 H1 0 N2 · 2 H2 O}n( H3BTC为 1 ,3 ,5 -均苯三羧酸 ,C4 H1 0 N2 为哌嗪 ) ,通过 X射线单晶衍射、红外光谱和荧光光谱进行表征 ,并用 TGA研究了该配位聚合物的热稳定性 .晶体属三斜晶系 ,P1空间群 ,a=1 .0 5 43 7( 9) nm,b=1 . 0 5 485 ( 9) nm,c=0 .71 482 ( 5 ) nm,α=1 0 2 .462 3 ( 2 8)°,β=91 .3 5 0 0 ( 4 2 )°,γ=1 1 1 .0 1 86( 2 9)°,V=0 .72 0 1 8( 1 0 ) nm3,Mr=764.3 7,Dc=1 .762 g· cm- 3,Z=1 ,μ( Mo Kα) =1 .2 5 mm- 1 ,F( 0 0 0 ) =3 94,R=0 .0 3 0 7,w R=0 .0 81 5 .晶体的基本构建单元中包含 2个 Co( )中心、 2个配位的 HBTC分子和 6个配位的水分子 .基本构建单元通过相互链接形成具有“Z”型结构的一维配位聚合链 ,链间通过两种不同的氢键 ( O— H… O和 N— H… O)相互作用 ,进而形成具有三维骨架结构的微孔晶体 ,微孔大小为 0 .71 nm× 0 .82 nm.荧光光谱表明 ,常温下用λex=3 1 2 nm的光激发后 ,配位聚合物在 3 2The title complex {[Co 2(HBTC) 2(H 2O) 6]·C 4H 10N 2·2H 2O} n(H 3BTC=1,3,5-benzene-tricarboxylic acid, C 4H 10N 2=piperazine) was hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis(Mo Kα). The crystal structure belongs to triclinic system, space group P1 {with } a=1.054 37(9) nm, {b=1.054 85(9) nm}, {c=0.714 82(5) nm}, {α=102.462 3(28)°}, {β=}{91.350 0(42)°}, γ= 111.018 6(29)°, V=0.720 18(10) nm 3, M r=764.37, D c=1.762 g/cm 3, Z=1, {μ=}1.25 mm -1, F(000)=394. A total of 6 681 reflections were collected, of which 3 247 were unique. The structure was refined to R=0.030 7 and wR=0.081 5 for 2 673 observed reflections with I>2σ(I). The crystal structure consists of cobalt(Ⅱ)carboxylate of BTC, coordination water molecules and discrete piperazine and water molecules. Extension of the coordination geometry around two cobalt atoms(Co1 and Co2) and two HBTC ligands generates an infinite 1D coordination polymer chain. These coordination polymer chains are further interdigitated by two different intermolecular hydrogen bonds( O-H...O and N-H...O) to afford a 3D extended metal-organic networks with a channel dimension of ca. 0.71 nm×0^82 nm. The complex gives a strong fluorescent emission band at 329 nm(λ ex=312 nm) in the solid state at room temperature.

关 键 词：配位聚合物 钴配合物 水热合成 结构表征 荧光性质 氢键 1 3 5-均苯三羧酸 

分 类 号：O614.812[理学—无机化学] O641.4[理学—化学]