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Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

Mills, Harrison A. and Jones, Christopher G. and Anderson, Kierstyn P. and Ready, Austin D. and Djurovich, Peter I. and Khan, Saeed I. and Hohman, J. Nathan and Nelson, Hosea M. and Spokoyny, Alexander M. (2022) Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies. Chemistry of Materials, 34 (15). pp. 6933-6943. ISSN 0897-4756. doi:10.1021/acs.chemmater.2c01319. https://resolver.caltech.edu/CaltechAUTHORS:20220422-972321800

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Abstract

Herein, we report the use of sterically invariant carborane-based chalcogenols, containing exopolyhedral B–Se or B–S bonds, as ligands for the formation of photoluminescent copper(I)-based metal–organic chalcogenolate assemblies (MOCHAs). We show that precise tuning of the carborane dipole by changing the carborane isomer from meta to ortho allows for control over the MOCHA morphology and regulation of the resulting photophysical properties. Furthermore, microcrystal electron diffraction (MicroED) has been demonstrated as a powerful tool for metal chalcogenide structure elucidation. Through the use of MicroED, one of the isolated materials is determined to consist of zero-dimensional Cu₄(Se–C₂B₁₀H₁₁)₄ clusters with an unprecedented Cu₄Se₄ geometry.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.chemmater.2c01319DOIArticle
https://doi.org/10.26434/chemrxiv-2022-twzjwDOIDiscussion Paper
ORCID:
AuthorORCID
Mills, Harrison A.0000-0002-3621-9608
Jones, Christopher G.0000-0003-4308-1368
Anderson, Kierstyn P.0000-0002-0297-0727
Ready, Austin D.0000-0001-8051-7568
Djurovich, Peter I.0000-0001-6716-389X
Khan, Saeed I.0000-0002-8641-9413
Hohman, J. Nathan0000-0002-9777-6432
Nelson, Hosea M.0000-0002-4666-2793
Spokoyny, Alexander M.0000-0002-5683-6240
Additional Information:© 2022 American Chemical Society. Received: May 2, 2022; Revised: June 22, 2022; Published: July 18, 2022. This work was supported by NSF Grants CHE-1846849 (NSF CAREER Award to A.M.S.) and DGE-1650604. H.A.M. is a recipient of the UCLA Dissertation Year Fellowship and the M. Frederick Hawthorne Inorganic Chemistry Dissertation Award. A.M.S. thanks Dreyfus Foundation for the Camille Dreyfus Teacher Scholar Award. The authors declare no competing financial interest. Crystallographic data are available from the Cambridge Crystallographic Data Centre, under the reference number: CCDC 2121247 (A) MicroED crystallographic data for A (CIF).
Funders:
Funding AgencyGrant Number
NSFCHE-1846849
NSF Graduate Research FellowshipDGE-1650604
UCLAUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Subject Keywords:Diffraction, Ligands, Materials, Molecular structure, Morphology
Issue or Number:15
DOI:10.1021/acs.chemmater.2c01319
Record Number:CaltechAUTHORS:20220422-972321800
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220422-972321800
Official Citation:Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies. Harrison A. Mills, Christopher G. Jones, Kierstyn P. Anderson, Austin D. Ready, Peter I. Djurovich, Saeed I. Khan, J. Nathan Hohman, Hosea M. Nelson, and Alexander M. Spokoyny. Chemistry of Materials 2022 34 (15), 6933-6943; DOI: 10.1021/acs.chemmater.2c01319
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114421
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Apr 2022 18:57
Last Modified:12 Aug 2022 19:44

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