Probing the solvent dependent photophysics of fac-[Re(CO) 3(dppz-X2)Cl] (dppz-X2 = 11,12-X 2-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH3, H, F, Cl, CF3

Marina K. Kuimova; Wassim Z. Alsindi; Alexander J. Blake; E. Stephen Davies; Daniele J. Lampus; Pavel Matousek; Jonathan McMaster; Anthony W. Parker; Michael Towrie; Xue Zhong Sun; Claire Wilson; Michael W. George

doi:10.1021/ic800753f

Probing the solvent dependent photophysics of fac-[Re(CO) ₃(dppz-X₂)Cl] (dppz-X₂ = 11,12-X ₂-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH₃, H, F, Cl, CF₃

Marina K. Kuimova, Wassim Z. Alsindi, Alexander J. Blake, E. Stephen Davies, Daniele J. Lampus, Pavel Matousek, Jonathan McMaster, Anthony W. Parker, Michael Towrie, Xue Zhong Sun, Claire Wilson, Michael W. George

Research output: Journal Publication › Article › peer-review

59 Citations (Scopus)

Abstract

The results of electrochemical measurements, density-functional theory calculations, emission and time -resolved IR (TRIR) spectroscopic studies for fac-[ReCl(CO)₃(dppz-X₂)], (dppz = dipyrido[3,2-a:2′, 3′-c]phenazine; X = CH₃, H, F, Cl, CF₃) are reported. For all complexes the calculations show that the lowest unoccupied molecular orbital (LUMO) is a phenazine based orbital localized on the dppz ligand. We observe that three different excited states, IL ππ*, metal-to-ligand charge-transfer (MLCT) (phen), and MLCT (phz), are formed depending upon the substituent on the dppz ligand and on the nature of the solvent. This means that both the energy and the nature of the photophysically active state(s) can be tuned by both chemical modification of dppz ligand and solvent properties. The excited-state dynamics in these systems is directly related to the mechanism of the "light switch effect", and ps-TRIR has allowed a deeper insight into this mechanism by being able to directly monitor the change in the population of the higher lying emissive phen-type ³MLCT and IL ππ* states and the dark ³MLCT (phz) state depending on the different environmental factors.

Original language	English
Pages (from-to)	9857-9869
Number of pages	13
Journal	Inorganic Chemistry
Volume	47
Issue number	21
DOIs	https://doi.org/10.1021/ic800753f
Publication status	Published - 3 Nov 2008
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Kuimova, M. K., Alsindi, W. Z., Blake, A. J., Davies, E. S., Lampus, D. J., Matousek, P., McMaster, J., Parker, A. W., Towrie, M., Sun, X. Z., Wilson, C., & George, M. W. (2008). Probing the solvent dependent photophysics of fac-[Re(CO) ₃(dppz-X₂)Cl] (dppz-X₂ = 11,12-X ₂-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH₃, H, F, Cl, CF₃. Inorganic Chemistry, 47(21), 9857-9869. https://doi.org/10.1021/ic800753f

@article{cfbd7521fea44e88a8b48ef77d11a46f,

title = "Probing the solvent dependent photophysics of fac-[Re(CO) 3(dppz-X2)Cl] (dppz-X2 = 11,12-X 2-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH3, H, F, Cl, CF3",

abstract = "The results of electrochemical measurements, density-functional theory calculations, emission and time -resolved IR (TRIR) spectroscopic studies for fac-[ReCl(CO)3(dppz-X2)], (dppz = dipyrido[3,2-a:2′, 3′-c]phenazine; X = CH3, H, F, Cl, CF3) are reported. For all complexes the calculations show that the lowest unoccupied molecular orbital (LUMO) is a phenazine based orbital localized on the dppz ligand. We observe that three different excited states, IL ππ*, metal-to-ligand charge-transfer (MLCT) (phen), and MLCT (phz), are formed depending upon the substituent on the dppz ligand and on the nature of the solvent. This means that both the energy and the nature of the photophysically active state(s) can be tuned by both chemical modification of dppz ligand and solvent properties. The excited-state dynamics in these systems is directly related to the mechanism of the {"}light switch effect{"}, and ps-TRIR has allowed a deeper insight into this mechanism by being able to directly monitor the change in the population of the higher lying emissive phen-type 3MLCT and IL ππ* states and the dark 3MLCT (phz) state depending on the different environmental factors.",

author = "Kuimova, {Marina K.} and Alsindi, {Wassim Z.} and Blake, {Alexander J.} and Davies, {E. Stephen} and Lampus, {Daniele J.} and Pavel Matousek and Jonathan McMaster and Parker, {Anthony W.} and Michael Towrie and Sun, {Xue Zhong} and Claire Wilson and George, {Michael W.}",

year = "2008",

month = nov,

day = "3",

doi = "10.1021/ic800753f",

language = "English",

volume = "47",

pages = "9857--9869",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "21",

}

Kuimova, MK, Alsindi, WZ, Blake, AJ, Davies, ES, Lampus, DJ, Matousek, P, McMaster, J, Parker, AW, Towrie, M, Sun, XZ, Wilson, C & George, MW 2008, 'Probing the solvent dependent photophysics of fac-[Re(CO) ₃(dppz-X₂)Cl] (dppz-X₂ = 11,12-X ₂-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH₃, H, F, Cl, CF₃', Inorganic Chemistry, vol. 47, no. 21, pp. 9857-9869. https://doi.org/10.1021/ic800753f

TY - JOUR

T1 - Probing the solvent dependent photophysics of fac-[Re(CO) 3(dppz-X2)Cl] (dppz-X2 = 11,12-X 2-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH3, H, F, Cl, CF3

AU - Kuimova, Marina K.

AU - Alsindi, Wassim Z.

AU - Blake, Alexander J.

AU - Davies, E. Stephen

AU - Lampus, Daniele J.

AU - Matousek, Pavel

AU - McMaster, Jonathan

AU - Parker, Anthony W.

AU - Towrie, Michael

AU - Sun, Xue Zhong

AU - Wilson, Claire

AU - George, Michael W.

PY - 2008/11/3

Y1 - 2008/11/3

N2 - The results of electrochemical measurements, density-functional theory calculations, emission and time -resolved IR (TRIR) spectroscopic studies for fac-[ReCl(CO)3(dppz-X2)], (dppz = dipyrido[3,2-a:2′, 3′-c]phenazine; X = CH3, H, F, Cl, CF3) are reported. For all complexes the calculations show that the lowest unoccupied molecular orbital (LUMO) is a phenazine based orbital localized on the dppz ligand. We observe that three different excited states, IL ππ*, metal-to-ligand charge-transfer (MLCT) (phen), and MLCT (phz), are formed depending upon the substituent on the dppz ligand and on the nature of the solvent. This means that both the energy and the nature of the photophysically active state(s) can be tuned by both chemical modification of dppz ligand and solvent properties. The excited-state dynamics in these systems is directly related to the mechanism of the "light switch effect", and ps-TRIR has allowed a deeper insight into this mechanism by being able to directly monitor the change in the population of the higher lying emissive phen-type 3MLCT and IL ππ* states and the dark 3MLCT (phz) state depending on the different environmental factors.

AB - The results of electrochemical measurements, density-functional theory calculations, emission and time -resolved IR (TRIR) spectroscopic studies for fac-[ReCl(CO)3(dppz-X2)], (dppz = dipyrido[3,2-a:2′, 3′-c]phenazine; X = CH3, H, F, Cl, CF3) are reported. For all complexes the calculations show that the lowest unoccupied molecular orbital (LUMO) is a phenazine based orbital localized on the dppz ligand. We observe that three different excited states, IL ππ*, metal-to-ligand charge-transfer (MLCT) (phen), and MLCT (phz), are formed depending upon the substituent on the dppz ligand and on the nature of the solvent. This means that both the energy and the nature of the photophysically active state(s) can be tuned by both chemical modification of dppz ligand and solvent properties. The excited-state dynamics in these systems is directly related to the mechanism of the "light switch effect", and ps-TRIR has allowed a deeper insight into this mechanism by being able to directly monitor the change in the population of the higher lying emissive phen-type 3MLCT and IL ππ* states and the dark 3MLCT (phz) state depending on the different environmental factors.

UR - http://www.scopus.com/inward/record.url?scp=56649086611&partnerID=8YFLogxK

U2 - 10.1021/ic800753f

DO - 10.1021/ic800753f

M3 - Article

C2 - 18828588

AN - SCOPUS:56649086611

SN - 0020-1669

VL - 47

SP - 9857

EP - 9869

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Probing the solvent dependent photophysics of fac-[Re(CO) ₃(dppz-X₂)Cl] (dppz-X₂ = 11,12-X ₂-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH₃, H, F, Cl, CF₃

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