TY  - JOUR
AU  - Basuroy, Krishnayan
AU  - Velazquez Garcia, Jose
AU  - Storozhuk, Darina
AU  - Henning, Robert
AU  - Gosztola, David
AU  - Thekku Veedu, Sreevidya
AU  - Techert, Simone
TI  - Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor–bridge–acceptor dyad in nanosecond-time-scale
JO  - The journal of chemical physics
VL  - 158
IS  - 5
SN  - 0021-9606
CY  - Melville, NY
PB  - American Institute of Physics
M1  - PUBDB-2022-04558
SP  - 054304 
PY  - 2023
AB  - Two conformational polymorphs of a donor–bridge–acceptor (D-B-A) dyad, p-(CH<sub>3</sub>)<sub>2</sub>N-C<sub>6</sub>H<sub>4</sub>-(CH<sub>2</sub>)<sub>2</sub>-(<sub>1</sub>-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH<sub>3</sub>)<sub>2</sub>N-C<sub>6</sub>H<sub>4</sub>/DMA is connected through a bridging group (B), –CH<sub>2</sub>–CH<sub>2</sub>–, to the electron acceptor (A) moiety pyrene. Though molecular dyads like PyCHDMA have the potential to change solar energy into electrical current through the process of photoinduced intramolecular charge transfer (ICT), the major challenge is the real-time investigation of the photoinduced ICT process in crystals, necessary to design solid-state optoelectronic materials. The time-correlated single photon counting (TCSPC) measurements with the single crystals showed that the ICT state lifetime of the thermodynamic form, PyCHDMA1 (pyrene and DMA: axial), is ∼3 ns, whereas, for the kinetic form, PyCHDMA20 (pyrene and DMA: equatorial), it is ∼7 ns, while photoexcited with 375 nm radiation. The polymorphic crystals were photo-excited and subsequently probed with a pink Laue x-ray beam in time-resolved x-ray diffraction (TRXRD) measurements. The TRXRD results suggest that in the ICT state, due to electron transfer from the tertiary N-atom in DMA moiety to the bridging group and pyrene moiety, a decreased repulsion between the lone-pair and the bond-pair at N-atom induces planarity in the C–N–(CH<sub>3</sub>)<sub>2</sub> moiety, in both polymorphs. The Natural Bond Orbital calculations and partial atomic charge analysis by Hirshfeld partitioning also corroborated the same. Although the interfragment charge transfer (IFCT) analysis using the TDDFT results showed that for the charge transfer excitation in both conformers, the electrons were transferred from the DMA moiety to mostly the pyrene moiety, the bridging group has little role to play in that.
LB  - PUB:(DE-HGF)16
C6  - 36754826
UR  - <Go to ISI:>//WOS:000932399200007
DO  - DOI:10.1063/5.0134792
UR  - https://bib-pubdb1.desy.de/record/481739
ER  -