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 | |
| Publication status | Published - 15 Dec 2018 |
Funding
[a] A. K. Narsaria, C. F. Guerra, A. W. Ehlers, K. Lammertsma, F. M. Bickelhaupt Department of Chemistry and Pharmaceutical Sciences and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands E-mail: [email protected] or [email protected] [b] J. Poater ICREA, Barcelona, Spain [c] J. Poater Department of Inorganic and Organic Chemistry and IQTCUB, Universitat de Barcelona, Barcelona, Spain [d] C. F. Guerra Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, Leiden, The Netherlands [e] A. W. Ehlers Van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands [f] A. W. Ehlers, K. Lammertsma Department of Chemistry, University of Johannesburg, Auckland Park, Johannesburg 2006, South Africa E-mail: [email protected] [g] F. M. Bickelhaupt Institute of Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands E-mail: [email protected] Contract Grant sponsor: Ministerio de Economía y Competitividad; Contract Grant number: CTQ2016-77558-R; Contract Grant sponsor: Nederlandse Organisatie voor Wetenschappelijk Onderzoek; Contract Grant sponsor: Shell This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. © 2018 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc. 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 |
Keywords
- charge-transfer excitations
- density functional calculations
- design rules
- donor–acceptor systems
- NIR absorption
