Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Experimental and theoretical characterisation of phosphorescence from rhenium polypyridyl tricarbonyl complexes
AU - Thorp-Greenwood, Flora L.
AU - Platts, James A.
AU - Coogan, Michael
PY - 2014/1/8
Y1 - 2014/1/8
N2 - Synthetic, spectroscopic and theoretical methods are used to probe the photophysics of five rhenium polypyridyl tricarbonyl complexes, which exhibit strong phosphorescence behaviour. Particular focus is placed on the effect of polypyridyl ligand structure on absorption and emission properties, for instance by extending conjugation or by addition of electron donating groups. Experimental methods are performed in a consistent and controlled manner, thereby giving data that is ideally suited for comparison with theory. Modifications in ligand structure give rise to large changes in absorption energies, but rather smaller differences in emission. Density functional theory (DFT) and its time-dependent formulation (TD-DFT) perform rather better in predicting emission than absorption. The effect of environment on photo-physical properties was probed theoretically by protonating nitrogen(s) of dipyrido[3,2-a:2′,3′-c]phenazine. (dppz) This has a large effect on calculatedspectra and leads to more complex patterns of absorption and emission that require spin-orbit coupling to be included in DFT calculations for full explanation.
AB - Synthetic, spectroscopic and theoretical methods are used to probe the photophysics of five rhenium polypyridyl tricarbonyl complexes, which exhibit strong phosphorescence behaviour. Particular focus is placed on the effect of polypyridyl ligand structure on absorption and emission properties, for instance by extending conjugation or by addition of electron donating groups. Experimental methods are performed in a consistent and controlled manner, thereby giving data that is ideally suited for comparison with theory. Modifications in ligand structure give rise to large changes in absorption energies, but rather smaller differences in emission. Density functional theory (DFT) and its time-dependent formulation (TD-DFT) perform rather better in predicting emission than absorption. The effect of environment on photo-physical properties was probed theoretically by protonating nitrogen(s) of dipyrido[3,2-a:2′,3′-c]phenazine. (dppz) This has a large effect on calculatedspectra and leads to more complex patterns of absorption and emission that require spin-orbit coupling to be included in DFT calculations for full explanation.
KW - Rhenium
KW - Phosphorescence
KW - Charge transfer
KW - Density functional theory
U2 - 10.1016/j.poly.2013.09.033
DO - 10.1016/j.poly.2013.09.033
M3 - Journal article
VL - 67
SP - 505
EP - 512
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -