TY - JOUR
T1 - Enhancing two-photon uncaging sensitivity in symmetrical dimeric conjugated coumarin cages
T2 - Role of the coupling core
AU - Dubois, Victor
AU - Klausen, Maxime
AU - Castet, Frédéric
AU - Verlhac, Jean Baptiste
AU - Blanchard-Desce, Mireille
N1 - Funding Information:
We thank the University of Bordeaux for PhD fellowships to M.K. and V.D. M.B-D. acknowledges support from the Conseil Régional d'Aquitaine (Chaire d'excellence). Calculations were performed on the HPC resources of the Institut des Sciences Moléculaires, co-funded by the Nouvelle Aquitaine region, as well as on the MCIA (Mésocentre de Calcul Intensif Aquitain) facilities of the Université de Bordeaux and of the Université de Pau et des Pays de l'Adour. We thank Guillaume Clermont, Jonathan Daniel and Simon Plaize for technical assistance in synthesis and measurements.
Funding Information:
We thank the University of Bordeaux for PhD fellowships to M.K. and V.D. M.B-D. acknowledges support from the Conseil Régional d’Aquitaine (Chaire d’excellence). Calculations were performed on the HPC resources of the Institut des Sciences Moléculaires, co-funded by the Nouvelle Aquitaine region, as well as on the MCIA (Mésocentre de Calcul Intensif Aquitain) facilities of the Université de Bordeaux and of the Université de Pau et des Pays de l’Adour. We thank Guillaume Clermont, Jonathan Daniel and Simon Plaize for technical assistance in synthesis and measurements.
Publisher Copyright:
© 2023 Elsevier B.V.
PY - 2023/1/7
Y1 - 2023/1/7
N2 - A series of symmetrical conjugated dimeric coumarinyl cages has been synthesized by grafting 7-diethlyaminocoumarin (DEAC) cages via π-linkers onto different aromatic cores displaying various electronic character (electron-withdrawing: benzobisthiazole BBTz, electron-donating: carbazole or ambivalent: fluorenyl). Due to their symmetrical design, all conjugated dimeric derivatives showed enhanced two-photon absorption at 730 nm, the electron-withdrawing core leading to the highest response (over 3000 GM). All dimeric derivatives retained the uncaging ability of the DEAC cage, with a strong influence of the nature of the core on the uncaging quantum yield. While the fluorenyl core led to an uncaging quantum yield similar to DEAC, the BBTz core led to a twice larger uncaging quantum yield and the carbazole core to even larger uncaging quantum yield (60 %). As a result, both electron-donating and electron-withdrawing cores lead to symmetrical dimeric DEAC derivatives showing unprecedented two-photon uncaging photo-sensitivity (up to 550 GM).
AB - A series of symmetrical conjugated dimeric coumarinyl cages has been synthesized by grafting 7-diethlyaminocoumarin (DEAC) cages via π-linkers onto different aromatic cores displaying various electronic character (electron-withdrawing: benzobisthiazole BBTz, electron-donating: carbazole or ambivalent: fluorenyl). Due to their symmetrical design, all conjugated dimeric derivatives showed enhanced two-photon absorption at 730 nm, the electron-withdrawing core leading to the highest response (over 3000 GM). All dimeric derivatives retained the uncaging ability of the DEAC cage, with a strong influence of the nature of the core on the uncaging quantum yield. While the fluorenyl core led to an uncaging quantum yield similar to DEAC, the BBTz core led to a twice larger uncaging quantum yield and the carbazole core to even larger uncaging quantum yield (60 %). As a result, both electron-donating and electron-withdrawing cores lead to symmetrical dimeric DEAC derivatives showing unprecedented two-photon uncaging photo-sensitivity (up to 550 GM).
KW - Coumarins
KW - Photorelease
KW - Photosensitive Protecting Groups
KW - Two-Photon Absorption
KW - Uncaging
U2 - 10.1016/j.jphotochem.2023.114544
DO - 10.1016/j.jphotochem.2023.114544
M3 - Article
AN - SCOPUS:85146676901
SN - 1010-6030
VL - 438
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
M1 - 114544
ER -