Photochemistry of (η6-arene)Cr(CO)3 (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy

Ian P. Clark; Michael W. George; Gregory M. Greetham; Emma C. Harvey; Conor Long; Jennifer C. Manton; Mary T. Pryce

doi:10.1021/jp112168u

Photochemistry of (η⁶-arene)Cr(CO)₃ (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy

Ian P. Clark, Michael W. George, Gregory M. Greetham, Emma C. Harvey, Conor Long, Jennifer C. Manton, Mary T. Pryce

Research output: Journal Publication › Article › peer-review

21 Citations (Scopus)

Abstract

The photochemistry of (η⁶-methylbenzoate)Cr(CO)₃, (η⁶-naphthalene)Cr(CO)₃, and (η⁶- phenanthrene)Cr(CO)₃ in n-heptane solution was investigated by picosecond time-resolved infrared spectroscopy (TRIR). The observation of two transient IR features in the organic carbonyl region at 1681 and 1724 cm ^-1 following 400 nm excitation of (η⁶-methylbenzoate) Cr(CO)₃ confirms formation of two excited states which are classified as metal-to-arene charge transfer (MACT) and metal-to-CO charge transfer (MCCT), respectively. Time-dependent density functional theory calculations have been used to support these assignments. Population of the MCCT excited state results in a slow (150 ps) expulsion of one CO ligand. Excitation of (η⁶-naphthalene)Cr(CO)₃ or (η⁶- phenanthrene)Cr(CO)₃ at either 400 or 345 nm produced two excited states: the MCCT state results in CO loss, while the MACT excited state results in a change to the coordination mode of the polyaromatic ligands before relaxing to the parent complex. A comparison of the infrared absorptions observed following the population of the MACT excited state with those calculated for nonplanar polyaromatic intermediates provides a model for the reduced hapticity species.

Original language	English
Pages (from-to)	2985-2993
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	115
Issue number	14
DOIs	https://doi.org/10.1021/jp112168u
Publication status	Published - 14 Apr 2011
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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Clark, I. P., George, M. W., Greetham, G. M., Harvey, E. C., Long, C., Manton, J. C., & Pryce, M. T. (2011). Photochemistry of (η⁶-arene)Cr(CO)₃ (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy. Journal of Physical Chemistry A, 115(14), 2985-2993. https://doi.org/10.1021/jp112168u

Clark, Ian P. ; George, Michael W. ; Greetham, Gregory M. et al. / Photochemistry of (η⁶-arene)Cr(CO)₃ (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution : Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy. In: Journal of Physical Chemistry A. 2011 ; Vol. 115, No. 14. pp. 2985-2993.

@article{ccc1143ddb104e4a955e12c8c0b47fc4,

title = "Photochemistry of (η6-arene)Cr(CO)3 (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy",

abstract = "The photochemistry of (η6-methylbenzoate)Cr(CO)3, (η6-naphthalene)Cr(CO)3, and (η6- phenanthrene)Cr(CO)3 in n-heptane solution was investigated by picosecond time-resolved infrared spectroscopy (TRIR). The observation of two transient IR features in the organic carbonyl region at 1681 and 1724 cm -1 following 400 nm excitation of (η6-methylbenzoate) Cr(CO)3 confirms formation of two excited states which are classified as metal-to-arene charge transfer (MACT) and metal-to-CO charge transfer (MCCT), respectively. Time-dependent density functional theory calculations have been used to support these assignments. Population of the MCCT excited state results in a slow (150 ps) expulsion of one CO ligand. Excitation of (η6-naphthalene)Cr(CO)3 or (η6- phenanthrene)Cr(CO)3 at either 400 or 345 nm produced two excited states: the MCCT state results in CO loss, while the MACT excited state results in a change to the coordination mode of the polyaromatic ligands before relaxing to the parent complex. A comparison of the infrared absorptions observed following the population of the MACT excited state with those calculated for nonplanar polyaromatic intermediates provides a model for the reduced hapticity species.",

author = "Clark, {Ian P.} and George, {Michael W.} and Greetham, {Gregory M.} and Harvey, {Emma C.} and Conor Long and Manton, {Jennifer C.} and Pryce, {Mary T.}",

year = "2011",

month = apr,

day = "14",

doi = "10.1021/jp112168u",

language = "English",

volume = "115",

pages = "2985--2993",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

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Clark, IP, George, MW, Greetham, GM, Harvey, EC, Long, C, Manton, JC & Pryce, MT 2011, 'Photochemistry of (η⁶-arene)Cr(CO)₃ (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy', Journal of Physical Chemistry A, vol. 115, no. 14, pp. 2985-2993. https://doi.org/10.1021/jp112168u

Photochemistry of (η⁶-arene)Cr(CO)₃ (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy. / Clark, Ian P.; George, Michael W.; Greetham, Gregory M. et al.
In: Journal of Physical Chemistry A, Vol. 115, No. 14, 14.04.2011, p. 2985-2993.

Research output: Journal Publication › Article › peer-review

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T1 - Photochemistry of (η6-arene)Cr(CO)3 (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution

T2 - Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy

AU - Clark, Ian P.

AU - George, Michael W.

AU - Greetham, Gregory M.

AU - Harvey, Emma C.

AU - Long, Conor

AU - Manton, Jennifer C.

AU - Pryce, Mary T.

PY - 2011/4/14

Y1 - 2011/4/14

N2 - The photochemistry of (η6-methylbenzoate)Cr(CO)3, (η6-naphthalene)Cr(CO)3, and (η6- phenanthrene)Cr(CO)3 in n-heptane solution was investigated by picosecond time-resolved infrared spectroscopy (TRIR). The observation of two transient IR features in the organic carbonyl region at 1681 and 1724 cm -1 following 400 nm excitation of (η6-methylbenzoate) Cr(CO)3 confirms formation of two excited states which are classified as metal-to-arene charge transfer (MACT) and metal-to-CO charge transfer (MCCT), respectively. Time-dependent density functional theory calculations have been used to support these assignments. Population of the MCCT excited state results in a slow (150 ps) expulsion of one CO ligand. Excitation of (η6-naphthalene)Cr(CO)3 or (η6- phenanthrene)Cr(CO)3 at either 400 or 345 nm produced two excited states: the MCCT state results in CO loss, while the MACT excited state results in a change to the coordination mode of the polyaromatic ligands before relaxing to the parent complex. A comparison of the infrared absorptions observed following the population of the MACT excited state with those calculated for nonplanar polyaromatic intermediates provides a model for the reduced hapticity species.

AB - The photochemistry of (η6-methylbenzoate)Cr(CO)3, (η6-naphthalene)Cr(CO)3, and (η6- phenanthrene)Cr(CO)3 in n-heptane solution was investigated by picosecond time-resolved infrared spectroscopy (TRIR). The observation of two transient IR features in the organic carbonyl region at 1681 and 1724 cm -1 following 400 nm excitation of (η6-methylbenzoate) Cr(CO)3 confirms formation of two excited states which are classified as metal-to-arene charge transfer (MACT) and metal-to-CO charge transfer (MCCT), respectively. Time-dependent density functional theory calculations have been used to support these assignments. Population of the MCCT excited state results in a slow (150 ps) expulsion of one CO ligand. Excitation of (η6-naphthalene)Cr(CO)3 or (η6- phenanthrene)Cr(CO)3 at either 400 or 345 nm produced two excited states: the MCCT state results in CO loss, while the MACT excited state results in a change to the coordination mode of the polyaromatic ligands before relaxing to the parent complex. A comparison of the infrared absorptions observed following the population of the MACT excited state with those calculated for nonplanar polyaromatic intermediates provides a model for the reduced hapticity species.

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Clark IP, George MW, Greetham GM, Harvey EC, Long C, Manton JC et al. Photochemistry of (η⁶-arene)Cr(CO)₃ (arene = methylbenzoate, naphthalene, or phenanthrene) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy. Journal of Physical Chemistry A. 2011 Apr 14;115(14):2985-2993. doi: 10.1021/jp112168u