| 三个低维ZnⅡ-二膦酸配位聚合物的合成、结构及荧光性能研究 |
| Syntheses, Structures and Fluorescent Properties of Three Low-Dimensional ZnⅡ-Diphosphonate Coordination Polymers |
| 作者 | 单位 | E-mail | | 马奎蓉 | 江苏省低维材料化学重点建设实验室, 淮阴师范学院化学化工学院, 淮安 223300 | kuirongma@163.com | | 张宇 | 江苏省低维材料化学重点建设实验室, 淮阴师范学院化学化工学院, 淮安 223300 | | | 阚玉和 | 江苏省低维材料化学重点建设实验室, 淮阴师范学院化学化工学院, 淮安 223300 | | | 李荣清 | 江苏省低维材料化学重点建设实验室, 淮阴师范学院化学化工学院, 淮安 223300 | | | 胡华友 | 江苏省低维材料化学重点建设实验室, 淮阴师范学院化学化工学院, 淮安 223300 | |
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| 摘要: 通过引入第二配体2,2'-联吡啶(2,2'-bipyridine, bipy),在水热条件下得到3个低维ZnⅡ-二膦酸配位聚合物:[Zn1.5(H2L)(bipy)(H2O)]·3H2O (1),[Zn(H3L)(bipy)]2 (2),[Zn(H3L)(bipy)(H2O)]·H2O (3)(H5L=1-羟亚乙基-1,1-二膦酸,CH3C(OH)(PO3H2)2)。采用单晶X-射线衍射、粉末X-射线衍射(PXRD)、红外光谱(IR)、元素分析、热重(TG-DSC)等测试手段对产物的结构进行了表征。单晶X-射线衍射数据分析表明化合物1为一维梯形双链结构,结构中含有2个晶体学独立的锌离子,分别以四配位和六配位模式与配体连接。化合物2为O-P-O双桥连接三角双锥[ZnO3N2]而成的双核零维结构。化合物3为八面体[ZnO4N2]通过O-P-O单桥连接而成的一维链状结构。氢键和π-π堆积作用进一步将3个低维ZnⅡ-二膦酸化合物扩展为三维超分子。对化合物1~3进行荧光性能的研究,测试结果表明,3个化合物均发射出强度远大于配体bipy的荧光发射峰(λem=374 nm(1)、388 nm(2)、387 nm(3),λex=252 nm),该峰来源于第二配体bipy(λem=391 nm,λex=252 nm)分子内部的π*-π电荷转移。电化学测试结果显示3个化合物均表现出一步单电子氧化还原过程,与自由配体相比给电子能力增强,未来可作为空穴传输材料在光电领域得到应用。 |
| 关键词: ZnⅡ-二膦酸配位聚合物 晶体结构 荧光 |
| 基金项目: 国家自然科学基金(No.21202058),江苏省高校自然科学研究重大项目(No.12KJA15004),江苏省低维材料化学重点建设实验室开放课题 (No.JSKC13127),淮阴师范学院高级别科研项目培育基金(No.11HSGJBZ12)资助项目。 |
| Abstract: By introducing the second organic ligand 2,2'-bipy(bipy), three low-dimensional examples of Zn(Ⅱ)-diphosphonate coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L=CH3C(OH)(PO3H2)2), [Zn1.5(H2L)(bipy)(H2O)]·3H2O (1), [Zn(H3L)(bipy)]2 (2), [Zn(H3L)(bipy)(H2O)]·H2O (3), have been hydrothermally obtained and characterized by powder X-ray diffraction(PXRD), IR, elemental analysis, TG-DSC. The single-crystal X-ray diffractions show that compound 1 possesses one-dimensional ladder-like double chain structure with two unique Zn(Ⅱ) ions in 4-and 6-coordinated modes, respectively. Compound 2 displays zero-dimensional structure built from binuclear unit [ZnO3N2]2 by a double O-P-O bridge. Compound 3 also shows one-dimensional chain structure built from octahedron [ZnO4N2] by a single O-P-O bridge. Then H-bond or/and π-π interactions further expand the one-and zero-dimensional structures into the three-dimensional supramolecular frameworks. Fluorescent measurements reveal that the maximum emission peaks of 1~3 have a significant increase in intensity compared to that of the bipy ligand, centered at 374 nm for 1, 388 nm for 2 and 387 nm for 3, respectively. These peaks are mainly caused by intraligand π*-π emission state of the bipy ligand(λem=391 nm, λex=252 nm). All the three compounds indicate a one-electron oxidation process based on electrochemical measurements and the donor ability of 1~3 has gone up, compared with the H5L and the bipy ligands. CCDC: 1001967, 1; 1001968, 2; 1001969, 3. |
| Keywords: Zn(Ⅱ)-diphosphonate coordination polymers crystal structure fluorescence |
| 投稿时间：2014-05-23 修订日期：2014-07-21 |
| 摘要点击次数: 1843 |
| 全文下载次数: 1881 |
| 马奎蓉,张宇,阚玉和,李荣清,胡华友.三个低维ZnⅡ-二膦酸配位聚合物的合成、结构及荧光性能研究[J].无机化学学报,2014,30(11):2549-2558. |
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