A hole delocalization strategy: Photoinduced mixed-valence MLCT states featuring extended lifetimes

BM Aramburu-Trošelj, PS Oviedo… - Inorganic …, 2019 - ACS Publications
Inorganic Chemistry, 2019ACS Publications
Bimetallic trans-[RuII (tpm)(bpy)(μNC) RuII (L) 4 (CN)] 2+, where bpy is 2, 2′-bipyridine, tpm
is tris (1-pyrazolyl) methane and L= 4-methoxypyridine (MeOpy) or pyridine (py), was
examined using ultrafast vis-NIR transient absorption spectroscopy. Of great relevance are
the longest-lived excited states in the form of strongly coupled photoinduced mixed-valence
systems, which exhibit intense photoinduced absorptions in the NIR and are freely tunable
by the judicious choice of the coordination spheres of the metallic ions. Using the latter …
Bimetallic trans-[RuII(tpm)(bpy)(μNC)RuII(L)4(CN)]2+, where bpy is 2,2′-bipyridine, tpm is tris(1-pyrazolyl)methane and L = 4-methoxypyridine (MeOpy) or pyridine (py), was examined using ultrafast vis-NIR transient absorption spectroscopy. Of great relevance are the longest-lived excited states in the form of strongly coupled photoinduced mixed-valence systems, which exhibit intense photoinduced absorptions in the NIR and are freely tunable by the judicious choice of the coordination spheres of the metallic ions. Using the latter strategy, we succeeded in tailoring the excited state lifetimes of bimetallic complexes and, in turn, achieving significantly longer values relative to related monometallic complexes. Notable is the success in extending the lifetimes, when considering the higher density of vibrational states, as they are expected to facilitate nonradiative ground-state recovery.
ACS Publications
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