Effect of the Ancillary Ligand on the Performance of Heteroleptic Cu(I) Diimine Complexes as Dyes in Dye-Sensitized Solar Cells.

Content Provider	Europe PMC
Author	Franchi, Daniele Leandri, Valentina Pizzichetti, Angela RaffaellaPia Xu, Bo Hao, Yan Zhang, Wei Sloboda, Tamara Svanström, Sebastian Cappel, Ute B. Kloo, Lars Sun, Licheng Gardner, James M.
Copyright Year	2022
Abstract	A series of heterolepticCu(I) diimine complexes with differentancillary ligands and 6,6′-dimethyl-2,2′-bipyridine-4,4′-dibenzoicacid (dbda) as the anchoring ligand were self-assembled on TiO2 surfaces and used as dyes for dye-sensitized solar cells(DSSCs). The binding to the TiO2 surface was studied byhard X-ray photoelectron spectroscopy for a bromine-containing complex,confirming the complex formation. The performance of all complexeswas assessed and rationalized on the basis of their respective ancillaryligand. The DSSC photocurrent–voltage characteristics, incidentphoton-to-current conversion efficiency (IPCE) spectra, and calculatedlowest unoccupied molecular orbital (LUMO) distributions collectivelyshow a push–pull structural dye design, in which the ancillaryligand exhibits an electron-donating effect that can lead to improvedsolar cell performance. By analyzing the optical properties of thedyes and their solar cell performance, we can conclude that the presenceof ancillary ligands with bulky substituents protects the Cu(I) metalcenter from solvent coordination constituting a critical factor inthe design of efficient Cu(I)-based dyes. Moreover, we have identifiedsome components in the I–/I3–-based electrolyte that causes dissociation of the ancillary ligand,i.e., TiO2 photoelectrode bleaching. Finally, the detailedstudies on one of the dyes revealed an electrolyte–dye interaction,leading to a dramatic change of the dye properties when adsorbed onthe TiO2 surface.
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Journal	ACS Applied Energy Materials [ACS Appl Energy Mater]
Volume Number	5
DOI	10.1021/acsaem.1c02778
PubMed Central reference number	PMC8889538
Issue Number	2
PubMed reference number	35252772
e-ISSN	25740962
Language	English
Publisher	American Chemical Society
Publisher Date	2022-01-13
Access Restriction	Open
Rights License	Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). © 2022 The Authors. Published by American Chemical Society
Subject Keyword	DSSC diimine copper(I)complexes copper photosensitizers in situ assembling heteroleptic complexes hard X-ray photoelectron spectroscopy push−pull density functional theory calculation
Content Type	Text
Resource Type	Article
Subject	Energy Engineering and Power Technology Chemical Engineering Materials Chemistry Electrical and Electronic Engineering Electrochemistry