TY - JOUR
T1 - Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells
AU - Hattori, Shigeki
AU - Wada, Yuji
AU - Yanagida, Shozo
AU - Fukuzumi, Shunichi
PY - 2005/7/6
Y1 - 2005/7/6
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=21644458485&partnerID=8YFLogxK
U2 - 10.1021/ja0506814
DO - 10.1021/ja0506814
M3 - Article
AN - SCOPUS:21644458485
SN - 0002-7863
VL - 127
SP - 9648
EP - 9654
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 26
ER -