Long-lived charge-transfer state from B−N frustrated Lewis pairs enchained in supramolecular copolymers

Beatrice Adelizzi, Pongphak Chidchob, Naoki Tanaka, Brigitte A.G. Lamers, Stefan C.J. Meskers, Soichiro Ogi, Anja R.A. Palmans, Shigehiro Yamaguchi (Corresponding author), E. W. Meijer (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

77 Citations (Scopus)

Abstract

The field of supramolecular polymers is rapidly expanding; however, the exploitation of these systems as functional materials is still elusive. To become competitive, supramolecular polymers must display microstructural order and the emergence of new properties upon copolymerization. To tackle this, a greater understanding of the relationship between monomers’ design and polymer microstructure is required as well as a set of functional monomers that efficiently interact with one another to synergistically generate new properties upon copolymerization. Here, we present the first implementation of frustrated Lewis pairs into supramolecular copolymers. Two supramolecular copolymers based on π-conjugated O-bridged triphenylborane and two different triphenylamines display the formation of B−N pairs within the supramolecular chain. The remarkably long lifetime and the circularly polarized nature of the resulting photoluminescence emission highlight the possibility to obtain an intermolecular B−N charge transfer. These results are proposed to be the consequences of the enchainment of B−N frustrated Lewis pairs within 1D supramolecular aggregates. Although it is challenging to obtain a precise molecular picture of the copolymer microstructure, the formation of random blocklike copolymers could be deduced from a combination of optical spectroscopic techniques and theoretical simulation.

Original languageEnglish
Pages (from-to)16681-16689
Number of pages9
JournalJournal of the American Chemical Society
Volume142
Issue number39
DOIs
Publication statusPublished - 30 Sept 2020

Funding

The authors express their thanks to Prof. Dr. Shu Seki (Kyoto University), Dr. Nathan Van Zee, and Lafayette de Windt for fruitful discussions, Martin van Son for his support in film measurements, and Dr. Naoki Ando and Ms. Mika Sakai (Nagoya University) for their support in the synthesis of boron precursors. The work in The Netherlands received funding from The Netherlands Organization for Scientific Research (NWO-TOP PUNT Grant No. 10018944) and the Dutch Ministry of Education, Culture and Science (Gravitation Program 024.001.035). Beatrice Adelizzi received additional funding from the European Union’s Horizon 2020 research and innovation program (SmartSAST Grant No. 890479). The work in Japan received funding from JSPS KAKENHI grants (18H03909 and 18H05261).

FundersFunder number
NWO‐TOP PUNT10018944
Horizon 2020 Framework Programme890479
Japan Society for the Promotion of Science18H03909, 18H05261
Ministerie van Onderwijs, Cultuur en Wetenschap024.001.035
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Nagoya University

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