Primary processes in photophysics and photochemistry of a potential light-activated anti-cancer dirhodium complex
Photophysics and photochemistry of a potential light-activated cytotoxic dirhodium complex [Rh 2 (µ-O 2 CCH 3 ) 2 (bpy)(dppz)](O 2 CCH 3 ) 2 , where bpy = 2,2′-bipyridine, dppz = dipyrido[3,2-a:2′,3′-c]phenazine (Complex 1 or Rh2) in aqueous solutions was studied by means of stationary photolysis an...
Saved in:
Published in | Photochemical & photobiological sciences Vol. 23; no. 1; pp. 153 - 162 |
---|---|
Main Authors | , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Cham
Springer International Publishing
2024
|
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | Photophysics and photochemistry of a potential light-activated cytotoxic dirhodium complex [Rh
2
(µ-O
2
CCH
3
)
2
(bpy)(dppz)](O
2
CCH
3
)
2
, where bpy = 2,2′-bipyridine, dppz = dipyrido[3,2-a:2′,3′-c]phenazine (Complex
1
or Rh2) in aqueous solutions was studied by means of stationary photolysis and time-resolved methods in time range from hundreds of femtoseconds to microseconds. According to the literature, Complex
1
demonstrates both oxygen-dependent (due to singlet oxygen formation) and oxygen-independent cytotoxicity. Photoexchange of an acetate ligand to a water molecule was the only observed photochemical reaction, which rate was increased by oxygen removal from solutions. Photoexcitation of Complex
1
results in the formation of the lowest triplet electronic excited state, which lifetime is less than 10 ns. This time is too short for diffusion-controlled quenching of the triplet state by dissolved oxygen resulting in
1
O
2
formation. We proposed that singlet oxygen is produced by photoexcitation of weakly bound van der Waals complexes [Rh2…O
2
], which are formed in solutions. If this is true, no oxygen-independent light-induced cytotoxicity of Complex
1
exists. Residual cytotoxicity deaerated solutions are caused by the remaining [Rh2…O
2
] complexes.
Graphical abstract |
---|---|
Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1474-905X 1474-9092 |
DOI: | 10.1007/s43630-023-00509-y |