Structural control of the excited-state dynamics of bis(dipyrrinato)zinc complexes: self-assembling chromophores for light-harvesting architectures.
The replacement of the phenyl rings at the 5,5'-positions of a bis(dipyrrinato)zinc complex with mesityl groups transforms the molecule from a very weak emitter that deactivates rapidly after photoexcitation (Phif = 0.006; tau approximately 90 ps) to a highly fluorescent chromophore with a long-lived singlet excited state (Phif = 0.36; tau approximately 3 ns). The results demonstrate that steric constraints on aryl-ring internal rotation dramatically alter the excited-state properties of 5,5'-substituted bis(dipyrrinato)metal complexes. The insights establish the foundation for tuning the photophysical properties of these chromophores for use in diverse photochemical applications.
Sazanovich
Igor V
IV
Department of Chemistry, Washington University, St. Louis, Missouri 63130-4889, USA.
Kirmaier
Christine
C
Hindin
Eve
E
Yu
Lianhe
L
Bocian
David F
DF
Lindsey
Jonathan S
JS
Holten
Dewey
D