Premium
Engineering of Ruthenium(II) Photosensitizers with Non‐Innocent Oxyquinolate and Carboxyamidoquinolate Ligands for Dye‐Sensitized Solar Cells
Author(s) -
Ngo Ken T.,
Lee Nicholas A.,
Pinnace Sashari D.,
Rochford Jonathan
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605991
Subject(s) - ruthenium , dye sensitized solar cell , ligand (biochemistry) , chemistry , redox , photochemistry , denticity , photosensitizer , aryl , metal , energy conversion efficiency , atomic orbital , combinatorial chemistry , materials science , electron , inorganic chemistry , organic chemistry , catalysis , optoelectronics , electrode , alkyl , physics , biochemistry , receptor , quantum mechanics , electrolyte
An alternative approach to replacing the isothiocyantate ligands of the N3 photosensitizer with light‐harvesting bidentate ligands is investigated for application in dye‐sensitized solar cells (DSSCs). An in‐depth theoretical analysis has been applied to investigate the optical and redox properties of four non‐innocent ligand platforms, which is then corroborated with experiment. Taking advantage of the 5‐ and 7‐positions of 8‐oxyquinolate, or the carboxyaryl ring system of the N ‐arylcarboxy‐8‐amidoquinolate ligand, fluorinated aryl substituents are demonstrated as an effective means of tuning complex redox potentials and light‐harvesting properties. The non‐innocent character, resulting from mixing of both the central metal‐dπ and ligand‐π manifolds, generates hybrid metal–ligand frontier orbitals. These play a major role by contributing to the redox properties and visible electronic transitions, and promoting an improved power conversion efficiency in a Ru DSSC device featuring non‐innocent ligands.