联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位

doi:10.7517/j.issn.1674-0475.2013.02.004

影像科学与光化学 ›› 2013, Vol. 31 ›› Issue (2): 117-124.DOI: 10.7517/j.issn.1674-0475.2013.02.004

联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位

李春丽¹, 李彪¹, 王治华², 王华¹

1. 河南大学特种功能材料教育部重点实验室, 河南开封 475004;
2. 河南大学化学化工学院, 河南开封 475004

收稿日期:2012-12-12 修回日期:2012-12-26 出版日期:2013-03-15 发布日期:2013-03-15
通讯作者: 王华,男,E-mail:hwang@henu.edu.cn.
基金资助:
国家自然科学基金项目(21270255, 20972041); 省杰出青年基金(104100510011);校省部共建项目(SBGJ090506).

Syntheses of Bithiophene Bridged Bis-terpyridine, Protonation and Complexation with Metal Cations (M²⁺)

LI Chun-li¹, LI Biao¹, WANG Zhi-hua², WANG Hua¹

1. Key Lab for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004, Henan, P. R. China;
2. College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, Henan, P. R. China

Received:2012-12-12 Revised:2012-12-26 Online:2013-03-15 Published:2013-03-15

摘要/Abstract

摘要： 以2,5-二溴噻吩为底物, 经醛基化、Kröhnke吡啶合成反应、Suzuki偶联三步制备了联噻吩桥联双三联吡啶 (BTTPY,总产率13%).通过紫外吸收及荧光光谱研究了其在酸性介质中的质子化效应, BTTPY在乙酸和三氟乙酸中的吸收及荧光光谱较非质子溶剂中均有明显红移.借助紫外吸收滴定法研究了其与过渡金属离子(Ni²⁺、Zn²⁺、Cd²⁺、Cu²⁺)的配位作用.结果表明BTTPY可与这些金属离子形成1:1的配合物,原子力显微镜 (AFM)图像显示, BTTPY与铬离子所形成的配位聚合物主要呈现一维堆积.

关键词: 联噻吩桥联双三联吡啶, 合成, 质子化作用, 金属配位

Abstract: Bithiophene bridged bis-terpyridine (BTTPY) was synthesized in a total yield of 13%, via formylation, Kröhnke pyridine synthesis and Suzuki coupling with 2,5-dibromothiophene as raw material. UV-Vis and fluorescence spectra of BTTPY exhibit strong red shift in acetic acid and trifluoroacetic due to strong protonation. UV-Vis titration shows that complexation of BTTPY and M²⁺ (Ni²⁺, Zn²⁺, Cd²⁺, Cu²⁺) could be occurred with a coordination ratio of 1:1. AFM image displays that organometallic polymer could be formed through complexation of BTTPY and Cd²⁺.

Key words: bithiophene bridged bis-terpyridine, synthesis, protonation, metal coordination

中图分类号:

李春丽, 李彪, 王治华, 王华. 联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位[J]. 影像科学与光化学, 2013, 31(2): 117-124.

LI Chun-li, LI Biao, WANG Zhi-hua, WANG Hua. Syntheses of Bithiophene Bridged Bis-terpyridine, Protonation and Complexation with Metal Cations (M²⁺)[J]. Imaging Science and Photochemistry, 2013, 31(2): 117-124.

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联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位

Syntheses of Bithiophene Bridged Bis-terpyridine, Protonation and Complexation with Metal Cations (M²⁺)

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联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位

Syntheses of Bithiophene Bridged Bis-terpyridine, Protonation and Complexation with Metal Cations (M2+)

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Syntheses of Bithiophene Bridged Bis-terpyridine, Protonation and Complexation with Metal Cations (M²⁺)