% IMPORTANT: The following is UTF-8 encoded. This means that in the presence % of non-ASCII characters, it will not work with BibTeX 0.99 or older. % Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or % “biber”. @ARTICLE{Basuroy:481739, author = {Basuroy, Krishnayan and Velazquez Garcia, Jose and Storozhuk, Darina and Henning, Robert and Gosztola, David and Thekku Veedu, Sreevidya and Techert, Simone}, title = {{A}xial vs equatorial: {C}apturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor–bridge–acceptor dyad in nanosecond-time-scale}, journal = {The journal of chemical physics}, volume = {158}, number = {5}, issn = {0021-9606}, address = {Melville, NY}, publisher = {American Institute of Physics}, reportid = {PUBDB-2022-04558}, pages = {054304}, year = {2023}, abstract = {Two conformational polymorphs of a donor–bridge–acceptor (D-B-A) dyad, p-(CH$_3$)$_2$N-C$_6$H$_4$-(CH$_2$)$_2$-($_1$-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH$_3$)$_2$N-C$_6$H$_4$/DMA is connected through a bridging group (B), –CH$_2$–CH$_2$–, 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$_3$)$_2$ 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.}, cin = {FS-SCS}, ddc = {530}, cid = {I:(DE-H253)FS-SCS-20131031}, pnm = {633 - Life Sciences – Building Blocks of Life: Structure and Function (POF4-633) / 6G3 - PETRA III (DESY) (POF4-6G3) / SFB 1073 C02 - In-situ hochauflösende Untersuchung des aktiven Zustands bei der (photo-) elektrochemischen Wasserspaltung (C02) (240172646) / SFB 1073 B06 - Echtzeituntersuchungen der optischen Anregung in oligonuklearen Metallkomplexen mit schaltbaren Spin- und Ladungszuständen (B06) (240171831)}, pid = {G:(DE-HGF)POF4-633 / G:(DE-HGF)POF4-6G3 / G:(GEPRIS)240172646 / G:(GEPRIS)240171831}, experiment = {EXP:(DE-H253)P-P11-20150101}, typ = {PUB:(DE-HGF)16}, pubmed = {36754826}, UT = {WOS:000932399200007}, doi = {10.1063/5.0134792}, url = {https://bib-pubdb1.desy.de/record/481739}, }