Near-IR Emissive B-N Lewis Pair-Functionalized Anthracenes via Selective LUMO Extension in Conjugated Dimer and Polymer.

Autor: Zuo J; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Liu K; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Harrell J; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Fang L; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Piotrowiak P; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Shimoyama D; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Lalancette RA; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA., Jäkle F; Department of Chemistry, Rutgers, The State University-Newark, 73 Warren Street, Newark, NJ 07102, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Nov 04; Vol. 63 (45), pp. e202411855. Date of Electronic Publication: 2024 Sep 02.
DOI: 10.1002/anie.202411855
Abstrakt: Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B-N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self-sensitized reactivity toward O 2 to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the π-system of BDPA to a vinyl-substituted monomer, vinylene-bridged dimer, and a polymer with an average of 20 chromophores. The extension of π-conjugation results in largely reduced band gaps of 1.8 eV for the dimer and 1.7 eV for the polymer, the latter giving rise to NIR emission with a maximum at 731 nm and an appreciable quantum yield of 7 %. Electrochemical and computational studies reveal efficient delocalization of the lowest unoccupied molecular orbital (LUMO) along the pyridyl-anthracene-pyridyl axis, which results in effective electronic communication between BDPA units, selectively lowers the LUMO, and ultimately narrows the band gap. Time-resolved emission and transient absorption (TA) measurements offer insights into the pertinent photophysical processes. Extension of π-conjugation also slows down the self-sensitized formation of endoperoxides, while significantly accelerating the thermal release of singlet oxygen to regenerate the parent acenes.
(© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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