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Exploring the Optical and Electrochemical Properties of Homoleptic versus Heteroleptic Diimine Copper(I) Complexes
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Kemi, Tillämpad fysikalisk kemi. KTH, Skolan för kemivetenskap (CHE), Centra, Molekylär elektronik, CMD.
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Kemi, Tillämpad fysikalisk kemi. KTH, Skolan för kemivetenskap (CHE), Centra, Molekylär elektronik, CMD.
Uppsala Univ, Angstrom Lab, Dept Chem, Div Phys Chem,Ctr Mol Devices, Box 523, SE-75120 Uppsala, Sweden..
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Kemi, Organisk kemi. KTH, Skolan för kemivetenskap (CHE), Centra, Molekylär elektronik, CMD.ORCID-id: 0000-0003-2811-247X
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2019 (engelsk)Inngår i: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 58, nr 18, s. 12167-12177Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

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 pi-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.

sted, utgiver, år, opplag, sider
AMER CHEMICAL SOC , 2019. Vol. 58, nr 18, s. 12167-12177
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URN: urn:nbn:se:kth:diva-261306DOI: 10.1021/acs.inorgchem.9b01487ISI: 000486565600035PubMedID: 31483631Scopus ID: 2-s2.0-85072235085OAI: oai:DiVA.org:kth-261306DiVA, id: diva2:1359133
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Tilgjengelig fra: 2019-10-08 Laget: 2019-10-08 Sist oppdatert: 2019-11-20bibliografisk kontrollert

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Leandri, ValentinaPizzichetti, Angela Raffaella PiaFranchi, DanieleSun, LichengKloo, LarsGardner, James M.

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