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

doi:10.1002/jcc.25731

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 Journal › Article › Academic › peer-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 language	English
Pages (from-to)	2690-2696
Number of pages	7
Journal	Journal of Computational Chemistry
Volume	39
Issue number	32
Early online date	4 Dec 2018
DOIs	https://doi.org/10.1002/jcc.25731
Publication status	Published - 15 Dec 2018

Funding

This work is part of the Industrial Partnership Programme (IPP) “Computational sciences for energy research” which is part of the Netherlands Organisation for Scientific Research (NWO). This research program is cofinanced by Shell Global Solutions International B.V. J.P. thanks the Spanish MINECO (CTQ2016-77558-R and MDM-2017-0767).

Funders	Funder number
Shell
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad	CTQ2016-77558-R

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

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

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10.1002/jcc.25731

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

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.",

keywords = "charge-transfer excitations, density functional calculations, design rules, donor–acceptor systems, NIR absorption",

author = "Narsaria, \{Ayush K.\} and Jordi Poater and \{Fonseca Guerra\}, C{\'e}lia and Ehlers, \{Andreas W.\} and Koop Lammertsma and Bickelhaupt, \{F. Matthias\}",

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doi = "10.1002/jcc.25731",

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T2 - Controlling the HOMO–LUMO gap using quantitative molecular orbital theory

AU - Narsaria, Ayush K.

AU - Poater, Jordi

AU - Fonseca Guerra, Célia

AU - Ehlers, Andreas W.

AU - Lammertsma, Koop

AU - Bickelhaupt, F. Matthias

PY - 2018/12/15

Y1 - 2018/12/15

N2 - 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.

AB - 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.

KW - charge-transfer excitations

KW - density functional calculations

KW - design rules

KW - donor–acceptor systems

KW - NIR absorption

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JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 32

ER -

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

Abstract

Funding

UN SDGs

Keywords

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