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@ARTICLE{Basuroy:626302,
author = {Basuroy, Krishnayan and Velazquez-Garcia, J. and Techert,
Simone},
title = {{C}apturing photo-induced structural changes in a
donor–bridge–acceptor dyad crystal, that also exhibits
elastic bending under mechanical pressure, using
pump–probe photocrystallography},
journal = {Acta crystallographica / Section A},
volume = {80},
number = {a1},
issn = {0108-7673},
address = {Oxford [u.a.]},
publisher = {Blackwell},
reportid = {PUBDB-2025-01375},
pages = {e425},
year = {2024},
abstract = {Controlling different external stimuli to tune the
photophysical properties of purely organic molecular
crystals toward designing multifunctional materials remains
a challenge. Over the years, pyrene-based fluorophores owing
to their high charge carrier mobility, complex
photoelectronic characteristics in the excited state, and
high fluorescence quantum yield, have come up as an
attractive choice for researchers while designing
luminescent molecular crystals. Recently, we have employed a
pair of polymorphic D-B-A dyad crystals where electron-rich
N,N ¢-dimethylaniline (DMA) acts as an electron donor (D)
is attached to pyrene (Py) that acts as an acceptor (A),
through -CH2-CH2- group, to study photo-induced charge
transfer (PCT) mechanism by time-resolved pump-probe
photocrystallography [1]. These D-B-A dyads sometimes behave
like semiconductors and if designed properly can be useful
as an efficient means of charge transfer and the creation of
long-lived charge-separated states necessary for designing
smart optoelectronic materials. The light-driven processes
are mostly investigated in the D-B-A dyads due to the
obvious reason of the matching of UV-Vis radiation
wavelength with the electronic excitations and the need to
investigate the excited state electron/hole transfer akin to
the one observed in the naturalphotosynthesis process. For
the present study, one such D-B-A molecule with an aromatic
ring as the bridging (B) group has been employed (Fig. 1a).
Since, the aromatic ring in the bridging group has the
potential to play the role of a hopping station during
electron transfer from DMA moiety to pyrene, measurements at
different pump-probe delays were employed. The
TCSPCmeasurements show that the photoinduced transient
excited state is decaying bi-exponentially with a ~22ns long
intramolecular charge transfer (ICT) state and a long-lived
excimer state (~85ns) (Fig. 1b). The TDDFT calculations show
a spatially separated HOMO and LUMO with a HOMO-LUMO gap of
3.46 eV, suggesting the CT nature of the HOMO-LUMO
transition (Fig. 1c). The needle-shaped single crystals were
also exhibiting elastic bending up to ~49° upon pressing
with a needle (Fig. 1d). These single crystals were employed
for time-resolved photocrystallography measurements at the
BioCARS beamline at the APS using different pump-probe
delays, where a short 35ps laser pump pulse was followed by
a ~100ps X-ray probe pulse on the single crystals (Fig.
1e-f). The pump-probe photocrystallography datasets
collected at different pump-probe delays show very
interesting structural changes directly correlating the
photo-chemical processes in solid-state. The
photo-difference map from an 18ns pump-probe
photocrytallography dataset shows how atomic shifts take
place in a photo-induced, intramolecular charge-separated
state (Fig. 1g). The results will be also useful in
accessing the changes in the intermolecular interactions at
different pump-probe delays which in turn will help design
solid-state, smart materials.},
month = {Aug},
date = {2024-08-26},
organization = {34th Crystallographic Meeting, Padova
(Italy), 26 Aug 2024 - 30 Aug 2024},
cin = {FS-SCS},
ddc = {530},
cid = {I:(DE-H253)FS-SCS-20131031},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G2 - FLASH (DESY) (POF4-6G2) / 6G3 -
PETRA III (DESY) (POF4-6G3)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G2 /
G:(DE-HGF)POF4-6G3},
experiment = {EXP:(DE-H253)P-P11-20150101},
typ = {PUB:(DE-HGF)8 / PUB:(DE-HGF)16},
UT = {WOS:001397789000405},
doi = {10.1107/S2053273324095743},
url = {https://bib-pubdb1.desy.de/record/626302},
}