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Tuning the visible-NIR absorption of azulenocyanine-based photosensitizers

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Abstract

A new photosensitizer 1-WS55 (dyad) based on two dyes with excellent properties, azulenocyanine (1) and WS55, is proposed at the density functional theory level (M06/def2-SVP). 1 is a dye having a broad NIR absorption (~ 1000 nm), and WS55 is a metal-free organic dye that presents a huge photoelectric conversion efficiency (PCE) of 9.5%. The dyad presents a panchromatic absorption along the UV–Vis-NIR region. It exhibits two intense Q bands (880, 926 nm) in the NIR region, one strong band (672 nm) in the visible region, and several bands in 300–600 nm. Charge transfer bands in the dyad from 1 to WS55 were found in the visible region, which favors the adsorption on an anatase TiO2 surface. The interaction energies dyad (dye)-TiO2 were calculated as a periodic system and corrected by the basis set superposition error. These show better adsorption for the dyad than fragments 1 and WS55. The electron injection calculated from the dye (dyad) to TiO2 suggests an efficient solar energy conversion because of ΔGinj > 0.2 eV. Additionally, calculations performed for the reorganization energy of electrons and holes indicate that the dyad presents the highest charge mobility. In summary, the dyad proposed 1-WS55 constitutes an excellent candidate to be used as a potential photosensitizer for the DSSCs.

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Funding

We thank the financial support of ANID/Chile under Projects FONDECYT 1221072 (G. C.-J.), FONDECYT 1180565 (X. Z.), and FONDAP 15110019 (Y. H.-R.). It is grateful for the support of ANID/Chile by Program/Doctorado Becas Nacionales 2021/21210406 (M.Z.-A) and 2021/21210404 (K. G.-T.). Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02) of the Universidad de Chile.

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Authors and Affiliations

  1. Laboratory of Theoretical Chemistry, Faculty of Chemistry and Biology, University of Santiago de Chile (USACH), Santiago, Chile

    Kevin Granados-Tavera, Michael Zambrano-Angulo & Gloria Cárdenas-Jirón

  2. Departamento de Química Inorgánica, Facultad de Química y de Farmacia, Centro de Energía UC, Centro de Investigación en Nanotecnología y Materiales Avanzados CIEN-UC, Pontificia, Universidad Católica de Chile, Vicuña Mackenna 4860, Macul, Santiago, Chile

    Yoan Hidalgo-Rosa

  3. Instituto de Ciencias Químicas Aplicadas, Facultad de Ingeniería, Universidad Autónoma de Chile, Santiago, Chile

    Ximena Zarate

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  1. Kevin Granados-Tavera
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Contributions

Kevin Granados-Tavera: original draft, methodology, formal analysis.

Michael Zambrano-Angulo: original draft, methodology, formal analysis.

Yoan Hidalgo-Rosa: original draft, formal analysis.

Ximena Zarate: original draft, formal analysis.

Gloria Cárdenas-Jirón: Project administration, review and editing, methodology.

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Correspondence to Gloria Cárdenas-Jirón.

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Granados-Tavera, K., Zambrano-Angulo, M., Hidalgo-Rosa, Y. et al. Tuning the visible-NIR absorption of azulenocyanine-based photosensitizers. J Mol Model 28, 344 (2022). https://doi.org/10.1007/s00894-022-05329-y

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