XMHIM · Gold(I)-Containing Metallopolymers: Synthesis, Self-assembly, and Applications

Gold(I)-Containing Metallopolymers: Synthesis, Self-assembly, and Applications

Goals and key milestones: a) Literature reading and training on the preparation and analysis of metallopolymers. b) Design and synthesis of gold(I) metallopolymers c) Investigation of the self-assembly behaviour of the gold(I) metallopolymers d) Studies on the sensing and light-emitting applications of the gold(I) metallopolymers e) Summary and completion of experimental data and writing reports and manuscripts. f) Outreach activities Progress: Dr. He designed and synthesized a variety of gold(I) thiolate and alkynyl materials, as well as trinuclear gold(I) planar system. The above-mentioned milestones were encountered with some difficulties with respect to the solubility and self-assembly step (c). The issues were mainly due to the strong gold(I)-gold(I) interaction which do not lead to a suitable unimer-aggregate equilibrium for controlled self-assembly. During the 2nd year progress on related materials containing other metals such as copper(I), platinum(II) and palladium(II) was made. These assemble into promising fluorescent fiber-like structures. Towards the end of the stay in Bristol this work was transferred to a new Ph.D. student to allow completion and a publication is anticipated in 2017. In addition to the above work, Dr. He also obtained results in a different self-assembly project based on ideas to use crystalline homopolymers with charged end-groups for self-assembly. An exciting discovery was to find that they self-assemble into well-defined 2D platelets including controlled “patchy’ structures. This work has been performed with several different polymers, including poly(ferrocenyldimethylsilane), and polylactide. Although the self-assembly of crystalline block copolymers has been extensively investigated, the analogous behavior of crystalline homopolymers has not attracted much interest. Unlike the block copolymer with corona serving as the protection of nanomaterials in selective solvents, the nanomaterials self-assembled from homopolymer are not colloidally stable. The use of a charged group solves this problem. Moreover, the approach can be extended to different polymers. Outreach: Fellow was part of Bristol’s Bright Nights in 2014 and 2015 where the public was invited to learn about Science and Marie Curie projects. In addition, Dr. He presented 1 lecture in the graduate course “Recent Advances with Soft Nanomaterials” in the Department of Chemistry at the University of Bristol entitled “Directed Self-Assembly of Inorganic Nanoparticles”. Publications: 1) Xiaoming He, Rebekah Hailes. Ian Manners Self-assembled fibers based on Cu, Pd and Pt centers. Manuscript in Preparation 2) Xiaoming He, Ming-Siao Hsiao, Charlotte E. Boott, Robert L. Harniman, Ali Nazemi, Xiaoyu Li, Mitchell A. Winnik, Ian Manners*, “2D Assemblies from crystallizable homopolymers with charged termini” Nature Materials, 2016, NM16061825, accepted. 3) John Finnegan, Xiaoming He, Ian Manners “2D assemblies from fluorene polycarbonate” Manuscript in Preparation

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