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Structures, spectroscopic properties and redox potentials of quaterpyridyl Ru( ii ) photosensitizer and its derivatives for solar energy cell: a density functional study

Scalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans -[Ru( R L)(NCS) 2 ] ( R L = 4,4-di- R -4,4-bis(carboxylic acid)-2,2:6,2:6,2-quaterpyridine, R = H ( 1 ), Me ( 2 ), t Bu ( 3 ) and COOH... Full description

Journal Title: Physical Chemistry Chemical Physics 2011, Vol.13(32), pp.14481-14489
Main Author: Pan, Qing-jiang
Other Authors: Guo, Yuan-ru , Li, Li , Odoh, Samuel O. , Fu, Hong-gang , Zhang, Hong-xing
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ID: ISSN: 1463-9076 ; E-ISSN: 1463-9084 ; DOI: 10.1039/c1cp00030f
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title: Structures, spectroscopic properties and redox potentials of quaterpyridyl Ru( ii ) photosensitizer and its derivatives for solar energy cell: a density functional study
format: Article
creator:
  • Pan, Qing-jiang
  • Guo, Yuan-ru
  • Li, Li
  • Odoh, Samuel O.
  • Fu, Hong-gang
  • Zhang, Hong-xing
subjects:
  • Absorption Spectra
  • Cationic
  • Density
  • Electrode Potentials
  • Excitation
  • Ligands
  • Mathematical Analysis
  • Spectroscopy
  • Miscellaneous Sciences (So)
ispartof: Physical Chemistry Chemical Physics, 2011, Vol.13(32), pp.14481-14489
description: Scalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans -[Ru( R L)(NCS) 2 ] ( R L = 4,4-di- R -4,4-bis(carboxylic acid)-2,2:6,2:6,2-quaterpyridine, R = H ( 1 ), Me ( 2 ), t Bu ( 3 ) and COOH ( 4 ); R L = 4,4-di- R -4,4-bis(carboxylic acid)-cycloquaterpyridine, R = COOH ( 5 )). The geometries of the molecular ground, univalent cationic and triplet excited states of 15 were optimized. In complexes 14 , the quaterpyridine ligand retains its planarity in the molecular, cationic and excited states, although the CN-Ru angle representing the SCN Ru coordination approaches 180 in the univalent cationic and triplet excited states. The theoretically designed complex 5 displays a curved cycloquaterpyridine ligand with significantly distorted SCN Ru coordination. The electron spin density distributions reveal that one electron is removed from the Ru/NCS moieties upon oxidation and the triplet excited state is due to the Ru/NCS polypyridine charge transfer (MLCT/L'LCT). The experimental absorption spectra were well reproduced by the time-dependent DFT calculations. In the visible region, two MLCT/L'LCT absorption bands were calculated to be at 652 and 506 nm for 3 , agreeing with experimental values of 637 and 515 nm, respectively. The replacement of the R- group with -COOH stabilizes the lower-energy unoccupied orbitals of * character in the quaterpyridine ligand in 4 . This results in a large red shift for these two MLCT/L'LCT bands. In contrast, the lower-energy MLCT/L'LCT peak of 5 nearly disappears due to the introduction of cycloquaterpyridine ligand. The higher energy bands in 5 however become broader and more intense. As far as absorption in the visible region is concerned, the theoretically designed 5 may be a very promising sensitizer for DSSC. In addition, the redox potentials of 15 were calculated and discussed, in conjunction with photosensitizers such as cis -[Ru(L 1 ) 2 (X) 2 ] (L 1 = 4,4-bis(carboxylic acid)-2,2-bipyridine; X = NCS ( 6 ), Cl ( 7 ) and CN ( 8 )), cis -[Ru(L 1 ) 2 (NCS) 2 ] (L 1 = 4,7-bis(carboxylic acid)-1,10-phenanthroline, 9 ), [NH 4 ][Ru(L 2 )(NCS) 3 ] (L 2 = 4,4,4-tris(carboxylic acid)-2,2:6,2-terpyridine, 10 ) and [Ru(L 2 )(NCS) 3 ] ( 11 ).
language:
source:
identifier: ISSN: 1463-9076 ; E-ISSN: 1463-9084 ; DOI: 10.1039/c1cp00030f
fulltext: fulltext
issn:
  • 1463-9076
  • 1463-9084
  • 14639084
  • 14639076
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titleStructures, spectroscopic properties and redox potentials of quaterpyridyl Ru( ii ) photosensitizer and its derivatives for solar energy cell: a density functional study
creatorPan, Qing-jiang ; Guo, Yuan-ru ; Li, Li ; Odoh, Samuel O. ; Fu, Hong-gang ; Zhang, Hong-xing
ispartofPhysical Chemistry Chemical Physics, 2011, Vol.13(32), pp.14481-14489
identifier
descriptionScalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans -[Ru( R L)(NCS) 2 ] ( R L = 4,4-di- R -4,4-bis(carboxylic acid)-2,2:6,2:6,2-quaterpyridine, R = H ( 1 ), Me ( 2 ), t Bu ( 3 ) and COOH ( 4 ); R L = 4,4-di- R -4,4-bis(carboxylic acid)-cycloquaterpyridine, R = COOH ( 5 )). The geometries of the molecular ground, univalent cationic and triplet excited states of 15 were optimized. In complexes 14 , the quaterpyridine ligand retains its planarity in the molecular, cationic and excited states, although the CN-Ru angle representing the SCN Ru coordination approaches 180 in the univalent cationic and triplet excited states. The theoretically designed complex 5 displays a curved cycloquaterpyridine ligand with significantly distorted SCN Ru coordination. The electron spin density distributions reveal that one electron is removed from the Ru/NCS moieties upon oxidation and the triplet excited state is due to the Ru/NCS polypyridine charge transfer (MLCT/L'LCT). The experimental absorption spectra were well reproduced by the time-dependent DFT calculations. In the visible region, two MLCT/L'LCT absorption bands were calculated to be at 652 and 506 nm for 3 , agreeing with experimental values of 637 and 515 nm, respectively. The replacement of the R- group with -COOH stabilizes the lower-energy unoccupied orbitals of * character in the quaterpyridine ligand in 4 . This results in a large red shift for these two MLCT/L'LCT bands. In contrast, the lower-energy MLCT/L'LCT peak of 5 nearly disappears due to the introduction of cycloquaterpyridine ligand. The higher energy bands in 5 however become broader and more intense. As far as absorption in the visible region is concerned, the theoretically designed 5 may be a very promising sensitizer for DSSC. In addition, the redox potentials of 15 were calculated and discussed, in conjunction with photosensitizers such as cis -[Ru(L 1 ) 2 (X) 2 ] (L 1 = 4,4-bis(carboxylic acid)-2,2-bipyridine; X = NCS ( 6 ), Cl ( 7 ) and CN ( 8 )), cis -[Ru(L 1 ) 2 (NCS) 2 ] (L 1 = 4,7-bis(carboxylic acid)-1,10-phenanthroline, 9 ), [NH 4 ][Ru(L 2 )(NCS) 3 ] (L 2 = 4,4,4-tris(carboxylic acid)-2,2:6,2-terpyridine, 10 ) and [Ru(L 2 )(NCS) 3 ] ( 11 ).
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titleStructures, spectroscopic properties and redox potentials of quaterpyridyl Ru( ii ) photosensitizer and its derivatives for solar energy cell: a density functional study
descriptionScalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans -[Ru( R L)(NCS) 2 ] ( R L = 4,4-di- R -4,4-bis(carboxylic acid)-2,2:6,2:6,2-quaterpyridine, R = H ( 1 ), Me ( 2 ), t Bu ( 3 ) and COOH ( 4 ); R L = 4,4-di- R -4,4-bis(carboxylic acid)-cycloquaterpyridine, R = COOH ( 5 )). The geometries of the molecular ground, univalent cationic and triplet excited states of 15 were optimized. In complexes 14 , the quaterpyridine ligand retains its planarity in the molecular, cationic and excited states, although the CN-Ru angle representing the SCN Ru coordination approaches 180 in the univalent cationic and triplet excited states. The theoretically designed complex 5 displays a curved cycloquaterpyridine ligand with significantly distorted SCN Ru coordination. The electron spin density distributions reveal that one electron is removed from the Ru/NCS moieties upon oxidation and the triplet excited state is due to the Ru/NCS polypyridine charge transfer (MLCT/L'LCT). The experimental absorption spectra were well reproduced by the time-dependent DFT calculations. In the visible region, two MLCT/L'LCT absorption bands were calculated to be at 652 and 506 nm for 3 , agreeing with experimental values of 637 and 515 nm, respectively. The replacement of the R- group with -COOH stabilizes the lower-energy unoccupied orbitals of * character in the quaterpyridine ligand in 4 . This results in a large red shift for these two MLCT/L'LCT bands. In contrast, the lower-energy MLCT/L'LCT peak of 5 nearly disappears due to the introduction of cycloquaterpyridine ligand. The higher energy bands in 5 however become broader and more intense. As far as absorption in the visible region is concerned, the theoretically designed 5 may be a very promising sensitizer for DSSC. In addition, the redox potentials of 15 were calculated and discussed, in conjunction with photosensitizers such as cis -[Ru(L 1 ) 2 (X) 2 ] (L 1 = 4,4-bis(carboxylic acid)-2,2-bipyridine; X = NCS ( 6 ), Cl ( 7 ) and CN ( 8 )), cis -[Ru(L 1 ) 2 (NCS) 2 ] (L 1 = 4,7-bis(carboxylic acid)-1,10-phenanthroline, 9 ), [NH 4 ][Ru(L 2 )(NCS) 3 ] (L 2 = 4,4,4-tris(carboxylic acid)-2,2:6,2-terpyridine, 10 ) and [Ru(L 2 )(NCS) 3 ] ( 11 ).
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titleStructures, spectroscopic properties and redox potentials of quaterpyridyl Ru( ii ) photosensitizer and its derivatives for solar energy cell: a density functional study
authorPan, Qing-jiang ; Guo, Yuan-ru ; Li, Li ; Odoh, Samuel O. ; Fu, Hong-gang ; Zhang, Hong-xing
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abstractScalar relativistic density functional theory (DFT) has been used to explore the spectroscopic and redox properties of Ruthenium-type photovoltaic sensitizers, trans -[Ru( R L)(NCS) 2 ] ( R L = 4,4-di- R -4,4-bis(carboxylic acid)-2,2:6,2:6,2-quaterpyridine, R = H ( 1 ), Me ( 2 ), t Bu ( 3 ) and COOH ( 4 ); R L = 4,4-di- R -4,4-bis(carboxylic acid)-cycloquaterpyridine, R = COOH ( 5 )). The geometries of the molecular ground, univalent cationic and triplet excited states of 15 were optimized. In complexes 14 , the quaterpyridine ligand retains its planarity in the molecular, cationic and excited states, although the CN-Ru angle representing the SCN Ru coordination approaches 180 in the univalent cationic and triplet excited states. The theoretically designed complex 5 displays a curved cycloquaterpyridine ligand with significantly distorted SCN Ru coordination. The electron spin density distributions reveal that one electron is removed from the Ru/NCS moieties upon oxidation and the triplet excited state is due to the Ru/NCS polypyridine charge transfer (MLCT/L'LCT). The experimental absorption spectra were well reproduced by the time-dependent DFT calculations. In the visible region, two MLCT/L'LCT absorption bands were calculated to be at 652 and 506 nm for 3 , agreeing with experimental values of 637 and 515 nm, respectively. The replacement of the R- group with -COOH stabilizes the lower-energy unoccupied orbitals of * character in the quaterpyridine ligand in 4 . This results in a large red shift for these two MLCT/L'LCT bands. In contrast, the lower-energy MLCT/L'LCT peak of 5 nearly disappears due to the introduction of cycloquaterpyridine ligand. The higher energy bands in 5 however become broader and more intense. As far as absorption in the visible region is concerned, the theoretically designed 5 may be a very promising sensitizer for DSSC. In addition, the redox potentials of 15 were calculated and discussed, in conjunction with photosensitizers such as cis -[Ru(L 1 ) 2 (X) 2 ] (L 1 = 4,4-bis(carboxylic acid)-2,2-bipyridine; X = NCS ( 6 ), Cl ( 7 ) and CN ( 8 )), cis -[Ru(L 1 ) 2 (NCS) 2 ] (L 1 = 4,7-bis(carboxylic acid)-1,10-phenanthroline, 9 ), [NH 4 ][Ru(L 2 )(NCS) 3 ] (L 2 = 4,4,4-tris(carboxylic acid)-2,2:6,2-terpyridine, 10 ) and [Ru(L 2 )(NCS) 3 ] ( 11 ).
doi10.1039/c1cp00030f
pages14481-14489
date2011-08-04