Cassingham, Megan A;
Goh, Yang G;
McClure, Eric T;
Hodgkins, Taylor L;
Zhang, Weiguo;
Liang, Mingli;
Dawlaty, Jahan M;
... Melot, Brent C; + view all
(2023)
Polarizable Anionic Sublattices Can Screen Molecular Dipoles in Noncentrosymmetric Inorganic-Organic Hybrids.
ACS Applied Materials and Interfaces
10.1021/acsami.2c20648.
(In press).
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Abstract
We report the growth and photophysical characterization of two polar hybrid lead halide phases, methylenedianiline lead iodide and bromide, (MDA)Pb2I6 and (MDA)Pb2Br6, respectively. The phases crystallize in noncentrosymmetric space group Fdd2, which produces a highly oriented molecular dipole moment that gives rise to second harmonic generation (SHG) upon excitation at 1064 nm. While both compositions are isostructural, the size dependence of the SHG signal suggests that the bromide exhibits a stronger phase-matching response whereas the iodide exhibits a significantly weaker non-phase-matching signal. Similarly, fluorescence from (MDA)Pb2Br6 is observed around 630 nm below 75 K whereas only very weak luminescence from (MDA)Pb2I6 can be seen. We attribute the contrasting optical properties to differences in the character of the halide sublattice and postulate that the increased polarizability of the iodide ions acts to screen the local dipole moment, effectively reducing the local electric field in the crystals.
| Type: | Article |
|---|---|
| Title: | Polarizable Anionic Sublattices Can Screen Molecular Dipoles in Noncentrosymmetric Inorganic-Organic Hybrids |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acsami.2c20648 |
| Publisher version: | https://doi.org/10.1021/acsami.2c20648 |
| Language: | English |
| Additional information: | © 2023 The Authors. Published by American Chemical Society. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
| Keywords: | inorganic−organic hybrid, nonlinear optics, polarizability, second harmonic generation, solid-state emission |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10167695 |
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