Browse by author
Lookup NU author(s): Professor Marina FreitagORCiD
Full text for this publication is not currently held within this repository. Alternative links are provided below where available.
Copyright © 2019 American Chemical Society. Due to ligand scrambling, the synthesis and investigation of the properties of heteroleptic Cu(I) complexes can be a challenging task. In this work, we have studied the optical and electrochemical properties of a series of homoleptic complexes, such as [Cu(dbda)2]+, [Cu(dmp)2]+, [Cu(Br-dmp)2]+, [Cu(bcp)2]+, [Cu(dsbtmp)2]+, [Cu(biq)2]+, and [Cu(dap)2]+ in solution, and those of their heteroleptics [Cu(dbda)(dmp)]+, [Cu(dbda)(Br-dmp)]+, [Cu(dbda)(bcp)]+, [Cu(dbda)(dsbtmp)]+, [Cu(dbda)(biq)]+, [Cu(dbda)(dap)]+ adsorbed on the surface of anatase TiO2 (dbda = 6,6′-dimethyl-2,2′-bipyridine-4,4′-dibenzoic acid; dmp = 2,9-dimethyl-1,10-phenanthroline; Br-dmp = 5-bromo-2,9-dimethyl-1,10-phenanthroline; bcp = bathocuproine or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline; biq = 2,2′-biquinoline; dap = 2,9-dianisyl-1,10-phenanthroline). We show that the maximum absorption wavelengths of the heteroleptic complexes on TiO2 can be reasonably predicted from those of the homoleptic complexes in solution through a simple linear relation, whereas the prediction of their redox properties is less trivial. In the latter case, two different linear patterns emerge: one including the ligands bcp, biq, and dap and another one including the ligands dmp, Br-dmp, and dsbtmp. We offer an interpretation of the data based on the chemical structure of the ligands. On one hand, ligands bcp, biq, and dap possess a more extended π-conjugated system, which gives a more prominent contribution to the overall redox properties of the ligand dbda. On the other hand, the ligands dmp, Br-dmp, and dsbtmp are all phenanthroline-based containing alkyl substituents and contribute less than dbda to the overall redox properties.
Author(s): Leandri V, Pizzichetti ARP, Xu B, Franchi D, Zhang W, Benesperi I, Freitag M, Sun L, Kloo L, Gardner JM
Publication type: Article
Publication status: Published
Journal: Inorganic Chemistry
Year: 2019
Volume: 58
Issue: 18
Pages: 12167-12177
Print publication date: 16/09/2019
Online publication date: 04/09/2019
Acceptance date: 02/04/2018
ISSN (print): 0020-1669
ISSN (electronic): 1520-510X
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.inorgchem.9b01487
DOI: 10.1021/acs.inorgchem.9b01487
PubMed id: 31483631
Altmetrics provided by Altmetric
