The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

Joanne Dyer; Werner J. Blau; Colin G. Coates; Caitriona M. Creely; John D. Gavey; Michael W. George; David C. Grills; Sarah Hudson; John M. Kelly; Pavel Matousek; John J. McGarvey; Jonathan McMaster; Anthony W. Parker; Michael Towrie; Julia A. Weinstein

doi:10.1039/B212628A

The photophysics of fac-[Re(CO)₃(dppz)(py)]⁺ in CH₃CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study†

Joanne Dyer,^a Werner J. Blau,^b Colin G. Coates,^c Caitriona M. Creely,^b John D. Gavey,^a Michael W. George,*^a David C. Grills,^a Sarah Hudson,^b John M. Kelly,*^b Pavel Matousek,^d John J. McGarvey,*^c Jonathan McMaster,^a Anthony W. Parker,^d Michael Towrie^d and Julia A. Weinstein^a

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* Corresponding authors

^a School of Chemistry, University of Nottingham, University Park, Nottingham, UK

^b Department of Chemistry and Department of Physics, University of Dublin, Trinity College, Dublin 2, Ireland

^c School of Chemistry, The Queen's University of Belfast, David Keir Building, Stranmillis Road, Belfast, BT9 5AG, Northern Ireland

^d Central Laser Facility, CCLRC Rutherford Appleton Laboratory, Chilton, Oxfordshire, UK

Abstract

The photophysical properties of fac-[Re(CO)₃(dppz)(py)]⁺ (1, where dppz = dipyrido[3,2-a:2′,3′-c]phenazine) in CH₃CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (³IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a ³π→π*(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a ³π→π*(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being ³dπ(Re)→π*(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.

This article is part of the themed collection: In commemoration of Lord George Porter

Photochemical & Photobiological Sciences

The photophysics of fac-[Re(CO)₃(dppz)(py)]⁺ in CH₃CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study†

Abstract

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The photophysics of fac-[Re(CO)₃(dppz)(py)]⁺ in CH₃CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

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