Synergistic electronic coupling/cross-talk between the isolated metal halide units of zero dimensional heterometallic (Sb, Mn) halide hybrid with enhanced emission

Biswas, Anupam and Bakthavatsalam, Rangarajan and Das, Deep K. and Raavi, Sai Santosh Kumar and et al, . (2022) Synergistic electronic coupling/cross-talk between the isolated metal halide units of zero dimensional heterometallic (Sb, Mn) halide hybrid with enhanced emission. Journal of Materials Chemistry C, 10 (1). pp. 360-370. ISSN 2050-7526

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Abstract

Heterometallic 0D metal halide hybrids, consisting of more than one kind of metal halide unit, are anticipated to manifest synergistic effects on the photo-physical properties of the constituent metal halide units. Such architectures hold great promise for the design and development of function-targeted materials. However, heterometallic 0D hybrids, featuring isolated metal halide units, typically do not show any synergistic effects due to large inter-unit spatial separations that inhibit interactions/coupling between the constituent metal halide units. It remains challenging to design synthetic strategies that would support structural modifications to allow synergistic electronic coupling between the metal halide units in heterometallic 0D hybrids. Here, we report synthesis and characterization of heterometallic (Sb, Mn) 0D hybrid, namelyTris SbMnCl, with isolated MnCl5units, (Sb/Mn)Cl6units, dispersed in the organic ligand matrix and a layer of dynamic and networked water molecules. Steady-state and time-resolved emission spectra (TRES) analysis suggests strong synergistic interaction between the isolated metal halide units. Efficient energy transfer from the strongly absorbing Sb centers to emissive Mn centers results in the observed enhanced emission. Proton conductivity measurements together with first-principles calculations suggest the unique role of the networked water molecules in mediating the electronic coupling/energy transfer between the separated metal halide units inTris SbMnClhybrid. This report highlights the role of the structure/composition of the synthesized heterometallic 0D hybrid in attaining electronic dimensionality higher than 0D through synergistic electronic interaction between the isolated metal halide units. © The Royal Society of Chemistry 2021.

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IITH Creators:
IITH CreatorsORCiD
Raavi, Sai Santosh Kumarhttp://orcid.org/0000-0002-2496-9233
Item Type: Article
Additional Information: The authors acknowledge Milan K Bisai (NCL Pune), Dr J. Nithyanandhan (NCL Pune), Dr Partha Hazra (IISER Pune) for insightful discussion. This work was financially supported by DST Grant No. CRG/2019/000252. A. B. and R. B. acknowledges CSIR for Senior Research Fellowship. J. S. and S. D. acknowledge National Supercomputing Mission (NSM) for providing computing resources of ‘PARAM Brahma’ at IISER Pune, which is implemented by C-DAC and supported by the Ministry of Electronics and Information Technology (MeitY) and Department of Science and Technology (DST), Government of India.
Uncontrolled Keywords: Cross talks; Design and Development; Electronic coupling; Enhanced Emission; Heterometallics; Photophysical properties; Spatial separation; Synergistic effect; Water molecule; Zero-dimensional
Subjects: Physics
Divisions: Department of Chemistry
Department of Physics
Depositing User: . LibTrainee 2021
Date Deposited: 15 Jul 2022 11:31
Last Modified: 15 Jul 2022 11:31
URI: http://raiithold.iith.ac.in/id/eprint/9736
Publisher URL: http://doi.org/10.1039/d1tc04704c
OA policy: https://v2.sherpa.ac.uk/id/publication/25610
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