Molecular design of benzo[c][1,2,5]thiadiazole or thieno[3,4-d]pyridazine-based auxiliary acceptors through different anchoring groups in D-π-A-A framework: A DFT/TD-DFT study

Lala Adetia Marlina; Winarto Haryadi; Rathawat Daengngern; Harno Dwi Pranowo

doi:10.1016/j.jmgm.2022.108148

Molecular design of benzo[c][1,2,5]thiadiazole or thieno[3,4-d]pyridazine-based auxiliary acceptors through different anchoring groups in D-π-A-A framework: A DFT/TD-DFT study

J Mol Graph Model. 2022 Jun:113:108148. doi: 10.1016/j.jmgm.2022.108148. Epub 2022 Feb 10.

Authors

Lala Adetia Marlina¹, Winarto Haryadi², Rathawat Daengngern³, Harno Dwi Pranowo⁴

Affiliations

¹ Austrian-Indonesian Centre for Computational Chemistry (AIC), Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia; Department of Chemistry, Faculty of Mathematic and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia.
² Department of Chemistry, Faculty of Mathematic and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia.
³ Department of Chemistry, School of Science, King Mongkut's Institute of Technology Ladkrabang, Bangkok, 10520, Thailand; Integrated Applied Chemistry Research Unit, School of Science, King Mongkut's Institute of Technology Ladkrabang, Bangkok, 10520, Thailand.
⁴ Austrian-Indonesian Centre for Computational Chemistry (AIC), Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia; Department of Chemistry, Faculty of Mathematic and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia. Electronic address: harnodp@ugm.ac.id.

PMID: 35180574
DOI: 10.1016/j.jmgm.2022.108148

Abstract

Based on density functional theory (DFT) and time-dependent DFT (TD-DFT) methods, a novel series of D-π-A-A porphyrin sensitizers adsorbed on the TiO₂ cluster has been investigated. The D-π-A-A configurations contained a donor of iminodibenzyl, π-linker of Zn-porphyrin, and two kinds of auxiliary acceptors (labeled as BT and TP), as well as five types of anchoring groups. The ground-state geometries, electronics, optics, and charge transfer properties of all free dyes including injection driving force (ΔG^inj), regeneration energy (ΔG^reg), and light-harvesting efficiency (LHE) were calculated. Additionally, reorganization energy (λ_total), electron affinity (EA), and ionization potential (IP) were also reported to confirm the transport properties of the designed dye. Furthermore, the interfacial system of dye@(TiO₂)₄₈ was further discussed to reveal the complexation energy of the system by considering the adsorption energy (E_ads) between dyes and (TiO₂)₄₈. The results showed that the insertion of different auxiliary acceptors in the D-π-A-A motif and variations in the anchoring groups resulted in red-shift absorption along with the increase in photovoltaic properties. These results suggested that BT with the rhodanine-3-acetic acid group (BT4) and BT with 2-(1,1-dicyanomethylene)rhodanine group (BT5) and TP with the same rhodanine-3-acetic acid and 2-(1,1-dicyanomethylene)rhodanine groups (TP4 and TP5) had shown better properties among other candidates for DSSCs. BT4-BT5 and TP4-TP5 had pronounce effect on optical and charge transfer properties by showing small HOMO-LUMO gaps, red-shifted spectra (λ_max), greater LHE and ICT characters, and maximum-negative E_ads. Thus, our theoretical investigation using these auxiliary moieties can be helpful for the precise structural modifications and design for developing efficient dyes in dye-sensitized solar cells (DSSCs).

Keywords: Anchoring group; Auxiliary acceptors; D-π-A-A; DFT/TD-DFT; Light-harvesting efficiency.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Density Functional Theory
Models, Molecular
Molecular Structure
Pyridazines*
Solar Energy*
Thiadiazoles*

Substances

Pyridazines
Thiadiazoles