双Salamo型四肟配体构筑的锌(Ⅱ)配合物:合成,晶体结构和荧光性质
Two Znic (Ⅱ) Complexes Constructed from a Bis (salamo)-type Tetraoxime Ligand:Syntheses,Crystal Structures and Luminescence Properties
作者单位E-mail
杨玉华 兰州交通大学化学与生物工程学院, 兰州 730070  
郝静 兰州交通大学化学与生物工程学院, 兰州 730070  
董银娟 兰州交通大学化学与生物工程学院, 兰州 730070  
王刚 兰州交通大学化学与生物工程学院, 兰州 730070  
董文魁 兰州交通大学化学与生物工程学院, 兰州 730070 dongwk@126.com 
摘要: 通过二水乙酸锌(Ⅱ)和双Salamo型四肟配体6,6'-二乙氧基-双(2,2'-(乙二氧双(氮次甲基)))四酚(H4L)的配位反应,合成了2种锌(Ⅱ)配合物即:[Zn3(L)(OAc)2(H2O)](1)和[Zn3(L)(OAc)2(H2O)]·[Zn3(L)(OAc)2(CH3OH)(H2O)]·3CH3OH·H2O(2)。该类配合物含有2个Salamo型L4-配体和3个锌(Ⅱ)离子,其中2个锌(Ⅱ)原子位于Salamo型螯合单元的N2O2空腔内。[Zn(L)]螯合物中桥联的酚氧原子进一步和中心的锌(Ⅱ)原子配位。这类结构能通过2个桥联的乙酸根配体稳定,从而使配合物15达到电荷平衡。配合物有2种不同的几何构型即扭曲的三角双锥和四方锥(配合物1)或三角双锥和八面体(配合物2)。另外,配合物12在激发波长为340和337 nm时能发出强的绿光,其最大发射波长分别为531和536 nm。
关键词: 双Salamo型四肟配体  锌(Ⅱ)配合物  合成  晶体结构  荧光性质
基金项目: 国家自然科学基金(No.21361015)资助项目
Abstract: Two Zn (Ⅱ) complexes,[Zn3(L)(OAc)2(H2O)](1) and[Zn3(L)(OAc)2(H2O)]·[Zn3(L)(OAc)2(CH3OH)(H2O)]·3CH3OH·H2O (2) have been synthesized via the complexation of zinc (Ⅱ) acetate dihydrate with a bis (salamo)-type tetraoxime ligand H4L (H4L=6,6'-diethoxy-bis (2,2'-(ethylenedioxybis (nitrilomethylidyne))) tetraphenol).X-ray crystallographic analyses reveal formation of trinuclear structures consisting of two salamo-type L4- ligands and three Zn (Ⅱ) atoms as expected from the analytical data.Two of the three Zn (Ⅱ) atoms are located in the salamo-type L4- chelate moieties.The μ-phenoxo oxygen atoms of the[Zn (L)]chelates further coordinate to centre Zn (Ⅱ) atom.The trinuclear structure is probably stabilized by the two μ-acetato ligands,which neutralize the whole charge of the complexes 1 and 2.There are two kinds of coordination geometries (trigonal bipyramidal and square pyramidal or trigonal bipyramidal and octahedral geometries) in complexes 1 and 2.In addition,complexes 1 and 2 exhibit strong green emission λmax=531 and 536 nm when excited with 340 and 337 nm,respectively.
Keywords: bis (salamo)-type tetraoxime ligand  Zn(Ⅱ) complex  synthesis  crystal structure  luminescence property
投稿时间:2017-03-17 修订日期:2017-05-08
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杨玉华,郝静,董银娟,王刚,董文魁.双Salamo型四肟配体构筑的锌(Ⅱ)配合物:合成,晶体结构和荧光性质[J].无机化学学报,2017,33(7):1280-1292.
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