多金属氧簇与倍半硅氧烷簇构筑的簇-簇杂化分子的合成及自组装结构

doi:10.6023/A13080821

化学学报 ›› 2014, Vol. 72 ›› Issue (1): 61-68.DOI: 10.6023/A13080821 上一篇下一篇

所属专题：纪念南开大学化学学科创建100周年

研究论文

多金属氧簇与倍半硅氧烷簇构筑的簇-簇杂化分子的合成及自组装结构

侯占要, 胡敏标, 王维

南开大学化学学院功能高分子材料教育部重点实验室和高分子化学研究所合成软物质中心天津 300071

投稿日期:2013-08-06 发布日期:2013-09-24
通讯作者: 王维，E-mail：weiwang@nankai.edu.cn E-mail:weiwang@nankai.edu.cn
基金资助:
项目受国家自然科学基金（Nos. 21274069和21334003）与高分子物理与化学国家重点实验室开放研究基金资助.

Synthesis and Self-Assembled Structure of A Cluster-Cluster Hybrid Molecule Composed of POM and POSS Clusters

Hou Zhanyao, Hu Minbiao, Wang Wei

Center for Synthetic Soft Materials, The Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, Tianjin 300071

Received:2013-08-06 Published:2013-09-24
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21274069 and 21334003) and Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry.

文章分享

1. 多金属氧簇与倍半硅氧烷簇构筑的簇-簇杂化分子的合成及自组装结构.PDF(343KB)

摘要/Abstract

以Wells-Dawson型多金属氧簇(POM)与T₈型倍半硅氧烷簇(POSS)为构筑单元，通过点击化学反应制备了一种由共价键连接形成的、新型的纳米簇-簇杂化分子(POM-2POSS)，并采用核磁共振(NMR)、质谱(MS)和红外光谱(IR)对产物化学结构进行了表征. 由于两个POSS簇连接在POM簇的同一侧，分子呈现“V”形. 同时，利用X射线衍射(XRD)及透射电子显微镜(TEM)表征了簇-簇杂化分子在本体中通过自组装过程形成的超分子结构，结果表明该簇-簇杂化分子形成了有序的层状结构，周期仅为5.1 nm. 本研究获得结果对以这类纳米簇为构筑单元构筑新型杂化分子以及通过自组装过程形成的、有序超分子结构的新型杂化材料的设计及制备提供了一个新的思路.

关键词: 杂化分子, 多金属氧簇, 倍半硅氧烷簇, 点击化学, 自组装

Polyhedral oligosilsesquioxane (POSS) and polyoxometalate (POM) are two kinds of clusters having totally different physical and chemical properties. For instance, the POSS cluster dissolves in weakly polar solvents, such as toluene, while the POM cluster, encapsulated by tetrabutylammonium counterions, dissolves in strongly polar solvents, such as acetonitrile, meaning the strong incompatibility. Based on this reason and their fixed shape, a novel cluster-cluster hybrid molecule with a V-shaped molecular structure (POM-2POSS) was rationally designed by covalently linking the two POSS clusters on the one side of the POM cluster. In the experiment, a two-azido-containing organosilyl derivative of a Wells-Dawson-type POM cluster and a one-propargyl-containing derivative of a POSS cluster were prepared at first. Then, the cluster-cluster hybrid was successfully synthesized by Cu-catalyzed click reaction between the two azide groups in the one POM derivative and the two propargyl groups in the two POSS derivatives. The chemical structure of this hybrid molecule was carefully characterized by NMR, ESI-MS and IR. In view of their strong incompatibility and of the particular three-dimensional (3D) structure POM-2POSS was expected to be able to self-assemble into ordered supramolecular structures. In the sample preparation POM-2POSS was dissolved in acetonitrile with a concentration of 5 mg/mL, and then the solution was dropped onto silicon substrates to prepare the thin film samples, finally the thin film samples were annealed in an acetonitrile vapor for 14 d. The film on the silicon substrate was characterized by XRD. The thin film samples for TEM characterization were made at first by floating onto the water surface and then transferred onto copper mesh. The structural analyses clearly demonstrated that the hybrid molecule self-assembled into a highly ordered lamellar morphology with a 5.1 nm periodicity, smaller than those found in block copolymers with a similar molecular weight. Formation of the highly ordered morphology reflects a self-assembly process due to absence of intermolecular entanglements, while the sub-5 nm periodicity is because of the 3D structures of the two building blocks. The findings provide a new platform for understanding of the self-assembly of nano-clusters and for development of novel hybrid materials.

Key words: hybrids, polyoxometalates, polyhedral oligosilsesquioxanes, click reaction, self-assembly

引用此文

侯占要, 胡敏标, 王维. 多金属氧簇与倍半硅氧烷簇构筑的簇-簇杂化分子的合成及自组装结构[J]. 化学学报, 2014, 72(1): 61-68.

Hou Zhanyao, Hu Minbiao, Wang Wei. Synthesis and Self-Assembled Structure of A Cluster-Cluster Hybrid Molecule Composed of POM and POSS Clusters[J]. Acta Chimica Sinica, 2014, 72(1): 61-68.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Gómez-Romero, P.; Sanchez, C. Functional Hybrid Materials, Wiley-VCH, Weinheim, 2006.

[2] Kickelbick, G. Hybrid Materials: Synthesis, Characterization, and Applications, Wiley-VCH, Weinheim, 2007.

[3] Clément, S.; Kenneth, J. S.; Susumu, K. Chem. Soc. Rev. 2011, 40, 471.

[4] Sanchez, C.; Julián, B.; Belleville, P.; Popall, M. J. Mater. Chem. 2005, 15, 3559.

[5] Zhang, Z. L.; Horsch, M. A.; Lamm, M. H.; Glotzer, S. C. Nano Lett. 2003, 3, 1341.

[6] Glotzer, S. C.; Horsch, M. A.; Iacovella, C. R.; Zhang, Z. L.; Chan, E. R.; Zhang, X. Curr. Opin. Colloid Interface Sci. 2005, 10, 287.

[7] Šari?, A.; Bozorgui, B.; Cacciuto, A. J. Phys. Chem. B 2011, 115, 7182.

[8] Filion, L.; Marechal, M.; Oorschot, B. V.; Pelt, D.; Smallenburg, F.; Dijkstra, M. Phys. Rev. Lett. 2009, 103, 188302.

[9] Pradeep, C. P.; Misdrahi, M. F.; Li, F. Y.; Zhang, J.; Xu, L.; Long, D. L.; Liu, T. B.; Cronin, L. Angew. Chem., Int. Ed. 2009, 48, 8309.

[10] Han, Y. K.; Xiao, Y.; Zhang, Z. J.; Liu, B.; Zheng, P.; He, S. J.; Wang, W. Macromolecules 2009, 42, 6543.

[11] Hu, M. B.; Xia, N.; Yu, W.; Ma, C.; Tang, J.; Hou, Z. Y.; Zheng, P.; Wang, W. Polym. Chem. 2012, 3, 617.

[12] Landsmann, S.; Lizandara-Pueyo, C.; Polarz, S. J. Am. Chem. Soc. 2010, 132, 5315.

[13] Landsmann, S.; Wessig, M.; Schmid, M.; Cölfen, H.; Polarz, S. Angew. Chem., Int. Ed. 2012, 51, 5995.

[14] Hu, M. B.; Hou, Z. Y.; Xiao, Y.; Yu, W.; Ma, C.; Ren, L. J.; Zheng, P.; Wang, W. Langmuir 2013, 29, 5714.

[15] Wang, X. L.; Wang, Y. L.; Miao, W. K.; Hu, M. B.; Tang, J.; Yu, W.; Hou, Z. Y.; Zheng, P.; Wang, W. Langmuir 2013, 29, 6537.

[16] Yu, X. F.; Zhong, S.; Li, X. P.; Tu, Y. F.; Yang, S. G.; Van Horn, R. M.; Ni, C. Y.; Pochan, D. J.; Quirk, R. P.; Wesdemiotis, C.; Zhang, W. B.; Cheng, S. Z. D. J. Am. Chem. Soc. 2010, 132, 16741.

[17] Li, Y.; Zhang, W. B.; Hsieh, I.; Zhang, G. L.; Cao, Y.; Li, X. P.; Wesdemiotis, C.; Lotz, B.; Xiong, H. M.; Cheng, S. Z. D. J. Am. Chem. Soc. 2011, 133, 10712.

[18] Sun, H. J.; Tu, Y. F.; Wang, C. L.; Van Horn, R. M.; Tsai, C. C.; Graham, M. J.; Sun, B.; Lotz, B.; Zhang, W. B.; Cheng, S. Z. D. J. Mater. Chem. 2011, 21, 14240.

[19] Yu, X. F.; Zhang, W. B.; Yue, K.; Li, X. P.; Liu, H.; Xin, Y.; Wang, C. L.; Wesdemiotis, C.; Cheng, S. Z. D. J. Am. Chem. Soc. 2012, 134, 7780.

[20] Polyoxometalate Chemistry: From Topology via Self-Assembly to Applications, Eds.: Pope, M. T.; Müller, A., Springer, Netherlands, 2001.

[21] Special thematic issue on polyoxometalates: Chem. Rev. 1998, 98, 1–388.

[22] Proust, A.; Thouvenot, R.; Gouzerh, P. Chem. Commun. 2008, 1837.

[23] Dolbecq, A.; Dumas, E.; Mayer, C. R.; Mialane, P. Chem. Rev. 2010, 110, 6009.

[24] Proust, A.; Matt, B.; Villanneau, R.; Guillemot, G.; Gouzerh, P.; Izzet, G. Chem. Soc. Rev. 2012, 41, 7605.

[25] Marcella, B.; Mauro, C.; Gianfranco, S.; Alessandro, B. Adv. Synth. Catal. 2004, 346, 648.

[26] Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chem. Rev. 2010, 110, 2081.

[27] Tanaka, K.; Chujo, Y. J. Mater. Chem. 2012, 22, 1733.

[28] Odobel, F.; Severac, M.; Pellegrin, Y.; Blart, E.; Fosse, C.; Cannizzo, C.; Mayer, C. R.; Elliott, K. J.; Harriman, A. Chem. Eur. J. 2009, 15, 3130.

[29] Contant, R.; Klemperer, W. G.; Yaghi, O., In Inorganic Syntheses, Mc Graw-Hill, New York, 1990, Vol. 27, p. 104.

[30] Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004.

[31] Hamley, I. W. The Physics of Block Copolymers, Oxford University Press, Oxford, 1999.

多金属氧簇与倍半硅氧烷簇构筑的簇-簇杂化分子的合成及自组装结构

Synthesis and Self-Assembled Structure of A Cluster-Cluster Hybrid Molecule Composed of POM and POSS Clusters

PDF

补充材料

可视化

被引次数

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	胡立伟, 刘宪虎, 刘春太, 宋延林, 李明珠. 光子晶体结构色材料的自组装制备与应用^★[J]. 化学学报, 2023, 81(7): 809-819.
[2]	李兰英, 陶晴, 闻艳丽, 王乐乐, 郭瑞妍, 刘刚, 左小磊. 多聚腺嘌呤DNA探针及其生物传感应用^★[J]. 化学学报, 2023, 81(6): 681-690.
[3]	汤乔伟, 蔡小青, 殷大鹏, 孔华庭, 张祥志, 张继超, 闫庆龙, 诸颖, 樊春海. 基于点击化学的同步辐射X射线成像标签^★[J]. 化学学报, 2023, 81(5): 441-444.
[4]	李畅, 郑振东, 郑江南, 田瑞军. 基于可断裂双功能探针的糖蛋白分析^★[J]. 化学学报, 2023, 81(12): 1673-1680.
[5]	苏东芮, 任小康, 于沄淏, 赵鲁阳, 王天宇, 闫学海. 酪氨酸衍生物调控酶催化路径可控合成功能黑色素^★[J]. 化学学报, 2023, 81(11): 1486-1492.
[6]	溥旭, 李泽娟, 石隽秋, 朱云卿, 杜建忠. 器官靶向的聚合物核酸载体研究进展^★[J]. 化学学报, 2023, 81(10): 1438-1446.
[7]	Jamshid Kadirkhanov, 钟峰, 张文建, 洪春雁. 聚合诱导自组装制备多腔室囊泡以及成核链段中亲溶剂片段的影响[J]. 化学学报, 2022, 80(7): 913-920.
[8]	王志琴, 项博, 黄晓宇, 陆国林, 冯纯. 磷钨酸对对苯撑乙烯撑寡聚物-b-聚(2-乙烯基吡啶)自晶种行为的影响^※[J]. 化学学报, 2022, 80(3): 297-302.
[9]	殷东, 商宏怡, 余文浩, 向仕凯, 胡平, 赵可清, 冯春, 汪必琴. 三唑环修饰的苯并菲二羧酸酯和酰亚胺: 合成、液晶及凝胶性[J]. 化学学报, 2022, 80(10): 1376-1384.
[10]	金艳梅, 蒙叶, 李远, 史建华, 邓雷. 对称二环己基取代六元瓜环与3-吡啶甲酰肼的超分子自组装[J]. 化学学报, 2022, 80(1): 44-48.
[11]	王旭生, 杨胥, 陈春辉, 李红芳, 黄远标, 曹荣. 石墨烯量子点/铁基金属-有机骨架复合材料高效光催化二氧化碳还原^※[J]. 化学学报, 2022, 80(1): 22-28.
[12]	李卫华. 桥连对嵌段共聚物自组装的调控[J]. 化学学报, 2021, 79(2): 133-138.
[13]	赵晶晶, 张正中, 陈小浪, 王蓓, 邓近远, 张蝶青, 李和兴. 微波诱导组装CuS@MoS₂核壳纳米管及其光催化类芬顿反应研究[J]. 化学学报, 2020, 78(9): 961-967.
[14]	江金辉, 朱云卿, 杜建忠. 开环聚合诱导自组装的挑战与展望[J]. 化学学报, 2020, 78(8): 719-724.
[15]	尹岑, 王子宽, 刘丹, 彭展涛, 宋环君, 祝浩, 陈其伟, 吴凯. meso-四(对甲氧基苯基)卟啉钴在货币金属单晶表面的吸附与自组装研究[J]. 化学学报, 2020, 78(7): 695-702.