Acid-base properties of the N3 ruthenium(II) solar cell sensitizer: a combined experimental and computational analysis

被引：35

作者：

Pizzoli, Giuliano ^{[1
,2
,3
]}

Lobello, Maria Grazia ^{[1
,2
,3
]}

Carlotti, Benedetta ^{[2
,3
]}

Elisei, Fausto ^{[2
,3
]}

Nazeeruddin, Mohammad K. ^{[4
]}

Vitillaro, Giuseppe ^{[1
]}

De Angelis, Filippo ^{[1
]}

机构：

[1] Ist CNR Sci & Tecnol Mol, Computat Lab Hybrid Organ Photovolta CLHYO, I-06213 Perugia, Italy

[2] Univ Perugia, Dept Chem, I-06123 Perugia, Italy

[3] Univ Perugia, CEMIN, I-06123 Perugia, Italy

[4] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, Lab Photon & Interfaces, CH-1015 Lausanne, Switzerland

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 38期

关键词：

DENSITY-FUNCTIONAL THEORY; ABSORPTION-SPECTRUM; PK(A) DETERMINATION; EXCITED-STATES; TIO2; FILMS; DYE; ADSORPTION; SOLVATION; RU(4,4'-COOH-2,2'-BPY)(2)(NCS)(2); SPECTROSCOPY;

D O I：

10.1039/c2dt31340e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We report a combined spectro-photometric and computational investigation of the acid-base equilibria of the N3 solar cell sensitizer [Ru(dcbpyH(2))(2)(NCS)(2)] (dcbpyH(2) = 4,4'-dicarboxyl-2,2' bipyridine) in aqueous/ethanol solutions. The absorption spectra of N3 recorded at various pH values were analyzed by Single Value Decomposition techniques, followed by Global Fitting procedures, allowing us to identify four separate acid-base equilibria and their corresponding ground state pK(a) values. DFT/TDDFT calculations were performed for the N3 dye in solution, investigating the possible relevant species obtained by sequential deprotonation of the four dye carboxylic groups. TDDFT excited state calculations provided UV-vis absorption spectra which nicely agree with the experimental spectral shapes at various pH values. The calculated pK(a) values are also in good agreement with experimental data, within <1 pK(a) unit. Based on the calculated energy differences a tentative assignment of the N3 deprotonation pathway is reported.

引用

页码：11841 / 11848

页数：8

共 40 条

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