Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells

Shigeki Hattori, Yuji Wada, Shozo Yanagida, Shunichi Fukuzumi

Research output: Contribution to journalArticlepeer-review

288 Scopus citations

Abstract

The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N′](maleonitriledithiolato-S,S′)copper ([Cu(SP)(mmt)])0/-, bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)2]2+/+), and bis(1,10-phenanthroline)copper ([Cu(phen)2]2+/+) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)2]2+/+ < [Cu(SP)(mmt)]0/- < [Cu(dmp)2]2+/+, in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I 3-/I- couple. The light energy conversion efficiency (η) values under illumination of simulated solar light irradiation (100 mW/cm2) of DSSCs using [Cu(phen)2] 2+/+, [Cu(dmp)2]2+/+, and [Cu(SP)(mmt)] 0/- were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum η value (2.2%) was obtained for a DSSC using the [Cu(dmp)2] 2+/+ redox couple under the light irradiation of 20 mW/cm2 intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I3-/I- couple.

Original languageEnglish
Pages (from-to)9648-9654
Number of pages7
JournalJournal of the American Chemical Society
Volume127
Issue number26
DOIs
StatePublished - 6 Jul 2005

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