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

摘要

Principles are presented for the design of functional near-infrared (NIR) organic dye molecules composed of simple donor (D), spacer (pi), and acceptor (A) building blocks in a D-pi-A fashion. Quantitative Kohn-Sham molecular orbital analysis enables accurate fine-tuning of the electronic properties of the pi-conjugated aromatic cores by effecting their size, including silaaromatics, adding donor and acceptor substituents, and manipulating the D-pi-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-pi-A with a strong excited-state intramolecular charge transfer and a NIR absorption at 879 nm. (c) 2018 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.