Rational design of near-infrared absorbing organic dyes: Controlling the HOMO–LUMO gap using quantitative molecular orbital theory

Ayush K. Narsaria, Jordi Poater, Célia Fonseca Guerra, Andreas W. Ehlers, Koop Lammertsma*, F. Matthias Bickelhaupt

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Principles are presented for the design of functional near-infrared (NIR) organic dye molecules composed of simple donor (D), spacer (π), and acceptor (A) building blocks in a D-π-A fashion. Quantitative Kohn–Sham molecular orbital analysis enables accurate fine-tuning of the electronic properties of the π-conjugated aromatic cores by effecting their size, including silaaromatics, adding donor and acceptor substituents, and manipulating the D-π-A torsional angle. The trends in HOMO–LUMO gaps of the model dyes correlate with the excitation energies computed with time-dependent density functional theory at CAMY-B3LYP. Design principles could be developed from these analyses, which led to a proof-of-concept linear D-π-A with a strong excited-state intramolecular charge transfer and a NIR absorption at 879 nm.

Original languageEnglish
Pages (from-to)2690-2696
Number of pages7
JournalJournal of Computational Chemistry
Volume39
Issue number32
Early online date4 Dec 2018
DOIs
Publication statusPublished - 15 Dec 2018

Keywords

  • charge-transfer excitations
  • density functional calculations
  • design rules
  • donor–acceptor systems
  • NIR absorption

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