Re(I) 配合物作为杂化发光聚硅氧烷和硅橡胶的主链取代基和交联剂。

Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers.

机构信息

Institute of Chemistry, St Petersburg University, 198504 St. Petersburg, Russia.

Department of Chemistry, University of Eastern Finland, 80101 Joensuu, Finland.

出版信息

Molecules. 2021 Nov 14;26(22):6866. doi: 10.3390/molecules26226866.

DOI:10.3390/molecules26226866

PMID:34833958

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8620272/

Abstract

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane--dimethylsiloxane) (N-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)(MeCN)(5-(4-ethynylphenyl)-2,2'-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N-PDMS (Re1-PDMS), while [Re(CO)Cl(5,5'-diethynyl-2,2'-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties.

摘要

本研究专注于使用铜（I）催化的叠氮-炔环加成（CuAAC）合成杂化发光聚硅氧烷和接枝有机金属铼（I）配合物的硅橡胶。铼（I）配合物的设计包括使用二亚胺配体来创建 MLCT 发光中心，并在配体环境的外围引入三重 C≡C 键，以提供点击反应能力。合成了聚（3-叠氮丙基甲基硅氧烷-二甲基硅氧烷）（N-PDMS），以在聚硅氧烷链中引入叠氮功能。[Re(CO)(MeCN)(5-(4-乙炔基苯基)-2,2'-联吡啶)]OTf（Re1）发光配合物用于制备与 N-PDMS 的发光共聚物（Re1-PDMS），而[Re(CO)Cl(5,5'-二乙炔基-2,2'-联吡啶)]（Re2）用作 N-PDMS 的发光交联剂，以获得发光硅橡胶（Re2-PDMS）。对所得杂化聚合物材料的光物理性质的检查表明，铼（I）部分的发射轮廓保持不变，金属中心允许控制具有指定性质的基于聚硅氧烷的材料的创建。