A New Series of Sandwich-Type 5,5′-Biterphenylenes: Synthetic Challenge, Structural Uniqueness and Photodynamics

Ming Lun Pan, Chao Hsien Hsu, Yan Ding Lin, Wei Sen Chen, Bo Han Chen, Chih Hsuan Lu, Shang Da Yang, Mu Jeng Cheng, Pi Tai Chou, Yao Ting Wu

研究成果: Article同行評審

1 引文 斯高帕斯(Scopus)

摘要

A new series of biaryls, bi-linear-terphenylenes (BLTPs), were prepared using the tert-butyllithium-mediated cyclization as the key synthetic step. The three-dimensional structures of the studied compounds were verified using X-ray crystallography and DFT calculations. Tetraaryl(ethynyl)-substituted BLTPs are highly crowded molecules, and the internal rotation around the central C−C bond is restricted due to a high barrier (>50 kcal/mol). These structures contain several aryl/terphenylenyl/aryl sandwiches, where the through-space π-π (TSPP) interactions are strongly reflected in the shielding of 1H NMR chemical shifts, reduction of oxidation potentials, increasing aromaticity of the central six-membered ring and decreasing antiaromaticity of the four-membered rings in a terphenylenyl moiety based on NICS(0) and iso-chemical shielding surfaces. Despite the restricted C−C bond associated intramolecular TSPP interactions for BLTPs in the ground state, to our surprise, the electronic coupling between two linear terphenylenes (LTPs) in BLTPs in the excited state is weak, so that the excited-state behavior is dominated by the corresponding monomeric LTPs. In other words, all BLTPs undergo ultrafast relaxation dynamics via strong exciton-vibration coupling, acting as a blue-light absorber with essentially no emission.

原文English
文章編號e202303523
期刊Chemistry - A European Journal
30
發行號11
DOIs
出版狀態Published - 2024 2月 21

All Science Journal Classification (ASJC) codes

  • 催化
  • 一般化學
  • 有機化學

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