Fullerene binding effects in Al(III)/Zn(II) Porphyrin/Phthalocyanine photophysical properties and charge transport

Merlys Borges-Martínez; Nicolás Montenegro-Pohlhammer; Xiance Zhang; Diego E Galvez-Aranda; Victor Ponce; Jorge M Seminario; Gloria Cárdenas-Jirón

doi:10.1016/j.saa.2021.120740

Fullerene binding effects in Al(III)/Zn(II) Porphyrin/Phthalocyanine photophysical properties and charge transport

Spectrochim Acta A Mol Biomol Spectrosc. 2022 Mar 15:269:120740. doi: 10.1016/j.saa.2021.120740. Epub 2021 Dec 13.

Authors

Merlys Borges-Martínez¹, Nicolás Montenegro-Pohlhammer², Xiance Zhang³, Diego E Galvez-Aranda³, Victor Ponce³, Jorge M Seminario⁴, Gloria Cárdenas-Jirón⁵

Affiliations

¹ Laboratory of Theoretical Chemistry, Faculty of Chemistry and Biology, University of Santiago de Chile (USACH), 9170022, Santiago, Chile. Electronic address: merlys.borges@usach.cl.
² Laboratory of Theoretical Chemistry, Faculty of Chemistry and Biology, University of Santiago de Chile (USACH), 9170022, Santiago, Chile. Electronic address: nicolas.montenegro.p@usach.cl.
³ Department of Chemical Engineering, Texas A&M University, College Station, Texas, U.S.A.
⁴ Department of Chemical Engineering, Texas A&M University, College Station, Texas, U.S.A. Electronic address: seminario@tamu.edu.
⁵ Laboratory of Theoretical Chemistry, Faculty of Chemistry and Biology, University of Santiago de Chile (USACH), 9170022, Santiago, Chile. Electronic address: gloria.cardenas@usach.cl.

PMID: 34968837
DOI: 10.1016/j.saa.2021.120740

Abstract

We evaluate the fullerene C₆₀ binding effect; through the metal (Al) and through the ligand (Pc,TPP), on the photophysical and charge transport properties of M-porphyrin(TPP)/phthalocyanine(Pc) (M = Al(III), Zn(II)). We perform density functional theory (DFT) and time-dependent DFT calculations for the macrocycle-C₆₀ dyads, showing that all systems studied are thermodynamically favorable. The C₆₀ binding effect on the absorption spectrum is a red-shift of the Q and Soret (B) bands of TPPs and Pcs. The Pc-dyads show longer λ for Q bands (673 nm) than those with TPP (568 nm). AlTPP-C₆₀ and ZnTPP-C₆₀ show a more favorable electron injection to TiO₂ than the analogs Pcs, and the regeneration of the dye is preferred in AlTPP-C₆₀ and AlPc-C₆₀. Zero-bias conductance is computed (10^-4-10^-7 G₀) for the dyads using molecular junctions with Au(111)-based electrodes. When a bias voltage of around 0.6 V up to 1 V is applied, an increase in current is obtained for AlTPP-C₆₀ (10^-7 A), ZnTPP-C₆₀ (10^-7 A), and AlPc-C₆₀ (10^-8 A). Although there is not a unique trend in the behavior of the dyads, Pcs have better photophysical properties than TPPs and the latter are better in the charge transport. We conclude that AlTPP(ZnTPP)-C₆₀ dyads are an excellent alternative for designing new materials for dye-sensitized solar cells or optoelectronic devices.

Keywords: Charge transport; Fullerene; Phthalocyanine; Porphyrin; Solar cells.