Phosphorescent metallaknots of Au(I)- bis(acetylide) strands directed by Cu(I) π- coordination

• 成果类型: Article
• 署名作者: Huang, Ya - Zi; Yang, Raorao; Zhang, Liang; Chen, Zhong - Ning
• 署名单位: Chinese Academy of Sciences; Fujian Institute of Research on the Structure of Matter, CAS; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; East China Normal University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-13433
• DOI: 10.1073/pnas.2403721121
• 发表日期: 2024-09-24
• 关键词: template synthesis; chemical topology; trefoil knot; cluster; CONSTRUCTION; complexes; catalysis; polymers; gold(i); link

摘要

Knots containing metal atoms as part of their continuous strand backbone are termed as metallaknots. While several metallaknots have been synthesized through one- pot self- assembly, the designed synthesis of metallaknots by controlling the arrangement of entanglements and strands connectivity remains unexplored. Here, we report the synthesis of metallaknots composed with Au(I)- bis(acetylide) linkages and templated by Cu(I) ions. Varying the ratio of the building blocks results in the switchable formation of two trefoil knots with different stoichiometries and symmetries (C2 or D 3 ) and an entangled metalla- complex. While the entangled complex formed serendipitously, the strand ends can be subsequently linked through coordinative closure to generate a 41 metallaknot in a highly designable fashion. The comparable structural characteristics of resulting metalla- complexes allow us to probe the correlations between their topologies and photophysical properties, showing the backbone rigidity of knots endows complexes with excellent phosphorescent properties. This strategy, in conjunction with the coordinative closure approach, provides a straightforward route for the formation of highly phosphorescent metallaknots that were previously challenging to access.