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Title: Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor–bridge–acceptor dyad in nanosecond-time-scale

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0134792· OSTI ID:1970700
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]
  1. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  2. University of Chicago, IL (United States)
  3. Argonne National Laboratory (ANL), Lemont, IL (United States). Center for Nanoscale Materials
  4. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); University of Gottingen (Germany)
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Two conformational polymorphs of a donor–bridge–acceptor (D-B-A) dyad, p-(CH3)2N-C6H4-(CH2)2-(1-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH3)2N-C6H4/DMA is connected through a bridging group (B), –CH2–CH2–, 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–(CH3)2moiety, 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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Helmholtz Association of German Research Centres; Deutsches Elektronen-Synchrotron (DESY); German Research Foundation (DFG)
Grant/Contract Number:
AC02-06CH11357; 217133147/SFB 1073
OSTI ID:
1970700
Journal Information:
Journal of Chemical Physics, Vol. 158, Issue 5; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
donor-bridge-acceptor system
polymorphs
charge transfer
photocrystallography
photoinduced electron transfer