Ultrafast and efficient energy transfer in a one- and two-photon sensitized rhodamine-BODIPY dyad: a perspective for broadly absorbing photocages.

Autor:	Asido M; Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. burghardt@chemie.uni-frankfurt.de., Hamerla C; Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. burghardt@chemie.uni-frankfurt.de., Weber R; Institute of Organic Chemistry and Chemical Biology, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. heckel@uni-frankfurt.de., Horz M; Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. burghardt@chemie.uni-frankfurt.de., Niraghatam MS; Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. burghardt@chemie.uni-frankfurt.de., Heckel A; Institute of Organic Chemistry and Chemical Biology, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. heckel@uni-frankfurt.de., Burghardt I; Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. burghardt@chemie.uni-frankfurt.de., Wachtveitl J; Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue Straße 7, 60438 Frankfurt am Main, Germany. burghardt@chemie.uni-frankfurt.de.
Jazyk:	angličtina
Zdroj:	Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2022 Jan 19; Vol. 24 (3), pp. 1795-1802. Date of Electronic Publication: 2022 Jan 19.
DOI:	10.1039/d1cp04528h
Abstrakt:	In view of the demand for photoactivatable probes that operate in the visible (VIS) to near infrared (NIR) region of the spectrum, we designed a bichromophoric system based on a rhodamine fluorophore and a BODIPY photocage. Two-photon excited fluorescence (TPEF) measurements and quantum chemical calculations reveal excellent two-photon properties of the employed rhodamine derivative. Excitation of the rhodamine unit via a one- or two-photon process leads to excitation energy transfer (EET) onto the BODIPY part, which is followed by the liberation of the leaving group. Ultrafast transient absorption spectroscopy provides evidence for a highly efficient EET dynamics on a sub-500 femtosecond scale. Complementary quantum dynamical calculations using the multi-layer multiconfiguration time-dependent Hartree (ML-MCTDH) approach highlight the quantum coherent character of the EET transfer. Photorelease of p -nitroaniline (PNA) was investigated by UV/vis absorption spectroscopy by either excitation of the rhodamine or the BODIPY moiety. Even though a quantitative assessment of the PNA yield could not be achieved for this particular BODIPY cage, the present study provides a design principle for a class of photocages that can be broadly activated between 500 and 900 nm.
Databáze:	MEDLINE
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