Study on azobenzene-modified Pd(Ⅱ) catalyst for photoswitchable polymerization of isocyanide

Journal Information

J. Hefei Univ. Tech. (Nat. Sci.), Aug.2025, Vol.48 No.8: 1079-1084, 1091

DOI: 10.3969/j.issn.1003-5060.2025.08.011

Authors

HE Kai $ ^{1,2} $, ZHOU Li $ ^{1,2} $, ZHOU Xingyu $ ^{1,2} $, CHEN Kun $ ^{1,2} $

(1. School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, China; 2. Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei 230009, China)

Abstract and Keywords

Abstract: An azobenzene-modified Pd(Ⅱ) catalyst was synthesized for the polymerization of achiral and chiral isocyanide monomers. Due to the cis and trans photoisomerization of azobenzene moiety on the Pd(Ⅱ) catalysts, different catalytic behaviors during the polymerization process of isocyanide monomers under visible light or UV light (365 nm) irradiation were observed. The polymerization rates of achiral isocyanide monomer A-1 and chiral isocyanide monomers L-1 and D-1 under visible light irradiation were approximately six times higher than those under UV light irradiation. And the optical helical poly-L-1 $ _{100} $ and poly-D-1 $ _{100} $ were obtained by the polymerization of chiral isocyanide monomers L-1 and D-1 under visible light irradiation using the Pd(Ⅱ) catalyst as initiator, and the molar absorptivities( $ \Delta\varepsilon_{364} $) of the polymers could be up to -13.47 dm $ ^{3} $/(cm·mol) and 14.16 dm $ ^{3} $/(cm·mol), respectively.

Keywords: azobenzene; Pd(II) catalyst; photoswitchable; polyisocyanide; chiral polymer

作者信息

贺楷 $ ^{1,2} $，周丽 $ ^{1,2} $，周星宇 $ ^{1,2} $，陈坤 $ ^{1,2} $

(1. 合肥工业大学化学与化工学院, 安徽合肥 230009; 2. 合肥工业大学先进催化材料与反应工程安徽省重点实验室, 安徽合肥 230009)

摘要和关键词

摘要: 文章合成了一种偶氮苯基团修饰的$\mathrm{Pd}(\mathrm{II})$催化剂，用于引发非手性、手性异腈单体的聚合。由于$\mathrm{Pd}(\mathrm{II})$催化剂中偶氮苯基团在紫外光和可见光下的顺式和反式光异构化的特性，使其在可见光或紫外光（365 nm）照射下引发异腈单体聚合时表现出不同的催化行为。$\mathrm{Pd}(\mathrm{II})$催化剂引发非手性异腈单体A-1、手性异腈单体L-1和D-1聚合时，它们在可见光照射下聚合的反应速率常数约为紫外光照射下反应速率常数的6倍；$\mathrm{Pd}(\mathrm{II})$催化剂引发手性异腈单体L-1、D-1在可见光照射下聚合得到的聚合物$\mathrm{poly-L-1_{100}}$和$\mathrm{poly-D-1_{100}}$均具有光学活性，其摩尔吸光系数$(\Delta\varepsilon_{364})$分别为$-13.47$、$14.16\ \mathrm{dm}^{3}/(\mathrm{cm}\cdot\mathrm{mol})$。

关键词: 偶氮苯；Pd(Ⅱ)催化剂；光控；聚异腈；手性聚合物

Funding

安徽省自然科学基金资助项目（2008085MB51）；中央高校基本科研业务费专项资金资助项目（PA2021GDSK0064）

合肥工业大学学报(自然科学版)

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