X-ray transient absorption structural characterization of the3MLCT triplet excited state of cis-[Ru(bpy)2(py)2]2+

Elisa Borfecchia; Claudio Garino; Luca Salassa; Tiziana Ruiu; Diego Gianolio; Xiaoyi Zhang; Klaus Attenkofer; Lin X. Chen; Roberto Gobetto; Peter J. Sadler; Carlo Lamberti

doi:10.1039/c3dt32865a

X-ray transient absorption structural characterization of the³MLCT triplet excited state of cis-[Ru(bpy)₂(py)₂]²⁺

Elisa Borfecchia, Claudio Garino, Luca Salassa^*, Tiziana Ruiu, Diego Gianolio, Xiaoyi Zhang, Klaus Attenkofer, Lin X. Chen, Roberto Gobetto, Peter J. Sadler, Carlo Lamberti

^*Corresponding author for this work

Chemistry

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Abstract

The excited state dynamics and structure of the photochemically active complex cis-[Ru(bpy)₂(py)₂]²⁺ have been investigated using optical transient absorption (OTA) and X-ray transient absorption (XTA) spectroscopy, and density functional theory (DFT). Upon light-excitation in aqueous solution cis-[Ru(bpy)₂(py)₂]²⁺ undergoes ultrafast dissociation of one pyridine ligand to form cis-[Ru(bpy)₂(py)(H₂O)]²⁺. OTA measurements highlighted the presence of two major time components of 1700 ps and 130 ps through which the system decays to the ground-state and evolves towards the photoproduct. XTA data were acquired after 150 ps, 500 ps, and 3000 ps from laser excitation (λ_exc = 351 nm) and provided the transient structure of the³MLCT state corresponding to the longer time component in the OTA experiment. In excellent agreement with DFT, XTA shows that the³MLCT geometry is characterized by an elongation of the dissociating Ru–N(py) bond and a shortening of the trans Ru–N(bpy) bond with respect to the ground state. Conversely, calculations show that the³MC state has a highly distorted structure with Ru–N(py) bonds between 2.77–3.05 Å.

Original language	English (US)
Pages (from-to)	6564-6571
Number of pages	8
Journal	Journal of the Chemical Society. Dalton Transactions
Volume	42
Issue number	18
DOIs	https://doi.org/10.1039/c3dt32865a
State	Published - Mar 8 2013

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General Chemistry

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Borfecchia, E., Garino, C., Salassa, L., Ruiu, T., Gianolio, D., Zhang, X., Attenkofer, K., Chen, L. X., Gobetto, R., Sadler, P. J., & Lamberti, C. (2013). X-ray transient absorption structural characterization of the³MLCT triplet excited state of cis-[Ru(bpy)₂(py)₂]²⁺. Journal of the Chemical Society. Dalton Transactions, 42(18), 6564-6571. https://doi.org/10.1039/c3dt32865a

@article{4c86a439a08d4e2b85eb33601ee74344,

title = "X-ray transient absorption structural characterization of the3MLCT triplet excited state of cis-[Ru(bpy)2(py)2]2+",

abstract = "The excited state dynamics and structure of the photochemically active complex cis-[Ru(bpy)2(py)2]2+ have been investigated using optical transient absorption (OTA) and X-ray transient absorption (XTA) spectroscopy, and density functional theory (DFT). Upon light-excitation in aqueous solution cis-[Ru(bpy)2(py)2]2+ undergoes ultrafast dissociation of one pyridine ligand to form cis-[Ru(bpy)2(py)(H2O)]2+. OTA measurements highlighted the presence of two major time components of 1700 ps and 130 ps through which the system decays to the ground-state and evolves towards the photoproduct. XTA data were acquired after 150 ps, 500 ps, and 3000 ps from laser excitation (λexc = 351 nm) and provided the transient structure of the3MLCT state corresponding to the longer time component in the OTA experiment. In excellent agreement with DFT, XTA shows that the3MLCT geometry is characterized by an elongation of the dissociating Ru–N(py) bond and a shortening of the trans Ru–N(bpy) bond with respect to the ground state. Conversely, calculations show that the3MC state has a highly distorted structure with Ru–N(py) bonds between 2.77–3.05 {\AA}.",

author = "Elisa Borfecchia and Claudio Garino and Luca Salassa and Tiziana Ruiu and Diego Gianolio and Xiaoyi Zhang and Klaus Attenkofer and Chen, {Lin X.} and Roberto Gobetto and Sadler, {Peter J.} and Carlo Lamberti",

year = "2013",

month = mar,

day = "8",

doi = "10.1039/c3dt32865a",

language = "English (US)",

volume = "42",

pages = "6564--6571",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "18",

}

Borfecchia, E, Garino, C, Salassa, L, Ruiu, T, Gianolio, D, Zhang, X, Attenkofer, K, Chen, LX, Gobetto, R, Sadler, PJ & Lamberti, C 2013, 'X-ray transient absorption structural characterization of the³MLCT triplet excited state of cis-[Ru(bpy)₂(py)₂]²⁺', Journal of the Chemical Society. Dalton Transactions, vol. 42, no. 18, pp. 6564-6571. https://doi.org/10.1039/c3dt32865a

TY - JOUR

T1 - X-ray transient absorption structural characterization of the3MLCT triplet excited state of cis-[Ru(bpy)2(py)2]2+

AU - Borfecchia, Elisa

AU - Garino, Claudio

AU - Salassa, Luca

AU - Ruiu, Tiziana

AU - Gianolio, Diego

AU - Zhang, Xiaoyi

AU - Attenkofer, Klaus

AU - Chen, Lin X.

AU - Gobetto, Roberto

AU - Sadler, Peter J.

AU - Lamberti, Carlo

PY - 2013/3/8

Y1 - 2013/3/8

N2 - The excited state dynamics and structure of the photochemically active complex cis-[Ru(bpy)2(py)2]2+ have been investigated using optical transient absorption (OTA) and X-ray transient absorption (XTA) spectroscopy, and density functional theory (DFT). Upon light-excitation in aqueous solution cis-[Ru(bpy)2(py)2]2+ undergoes ultrafast dissociation of one pyridine ligand to form cis-[Ru(bpy)2(py)(H2O)]2+. OTA measurements highlighted the presence of two major time components of 1700 ps and 130 ps through which the system decays to the ground-state and evolves towards the photoproduct. XTA data were acquired after 150 ps, 500 ps, and 3000 ps from laser excitation (λexc = 351 nm) and provided the transient structure of the3MLCT state corresponding to the longer time component in the OTA experiment. In excellent agreement with DFT, XTA shows that the3MLCT geometry is characterized by an elongation of the dissociating Ru–N(py) bond and a shortening of the trans Ru–N(bpy) bond with respect to the ground state. Conversely, calculations show that the3MC state has a highly distorted structure with Ru–N(py) bonds between 2.77–3.05 Å.

AB - The excited state dynamics and structure of the photochemically active complex cis-[Ru(bpy)2(py)2]2+ have been investigated using optical transient absorption (OTA) and X-ray transient absorption (XTA) spectroscopy, and density functional theory (DFT). Upon light-excitation in aqueous solution cis-[Ru(bpy)2(py)2]2+ undergoes ultrafast dissociation of one pyridine ligand to form cis-[Ru(bpy)2(py)(H2O)]2+. OTA measurements highlighted the presence of two major time components of 1700 ps and 130 ps through which the system decays to the ground-state and evolves towards the photoproduct. XTA data were acquired after 150 ps, 500 ps, and 3000 ps from laser excitation (λexc = 351 nm) and provided the transient structure of the3MLCT state corresponding to the longer time component in the OTA experiment. In excellent agreement with DFT, XTA shows that the3MLCT geometry is characterized by an elongation of the dissociating Ru–N(py) bond and a shortening of the trans Ru–N(bpy) bond with respect to the ground state. Conversely, calculations show that the3MC state has a highly distorted structure with Ru–N(py) bonds between 2.77–3.05 Å.

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U2 - 10.1039/c3dt32865a

DO - 10.1039/c3dt32865a

M3 - Article

C2 - 23474490

AN - SCOPUS:84875185937

SN - 1477-9226

VL - 42

SP - 6564

EP - 6571

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 18

ER -

X-ray transient absorption structural characterization of the³MLCT triplet excited state of cis-[Ru(bpy)₂(py)₂]²⁺

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