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Article: Kinetically Controlled Self-assembly Of Phosphorescent Auiii Aggregates And Ligand-to-metal–metal Charge Transfer Excited State: A Combined Spectroscopic And DFT/TDDFT Study
Title | Kinetically Controlled Self-assembly Of Phosphorescent Auiii Aggregates And Ligand-to-metal–metal Charge Transfer Excited State: A Combined Spectroscopic And DFT/TDDFT Study |
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Authors | |
Keywords | Platinum Phosphorescence Ligands |
Issue Date | 2019 |
Publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html |
Citation | Journal of the American Chemical Society, 2019, v. 141 n. 29, p. 11572-11582 How to Cite? |
Abstract | Metallophilic interactions in d10–d10(AuI–AuI)/d8–d8(PtII–PtII, RhI–RhI, IrI–IrI) complexes have been widely studied for decades, and metal–metal (M–M) bonding character has been revealed in both the ground and excited states. These M–M closed-shell interactions are appealing driving forces for the self-assembly of supramolecular/polymeric systems, providing luminescent properties distinctly different from those of the corresponding monomer. However, reports on attractive interactions between two AuIII complex cations are scarce in the literature. Herein is described a series of pincer-type cationic AuIII complexes with different auxiliary ligands, among which the AuIII–allenylidene complex displays a close Au–Au contact of 3.367 Å between neighboring molecules in its X-ray crystal structure; AuIII–isocyanide complexes show a broad red-shifted absorption band and prominent phosphorescence upon aggregation that was influenced by an attractive AuIII–AuIII bonding interaction in the excited state; and AuIII–acetylene complexes can undergo living supramolecular polymerization upon varying the counteranion. The nature of the emissive excited state(s) of the AuIII aggregates is assigned to a mixture of major 3[π–π*] and minor 3LMMCT (ligand-to-metal–metal charge transfer) states based on combined spectroscopic and DFT/TDDFT studies. The morphology of the AuIII aggregates is highly dependent on the concentration and nature of the counteranion. A qualitative model has been applied to account for the concentration- and counteranion-dependent kinetics of the supramolecular polymerization process. |
Persistent Identifier | http://hdl.handle.net/10722/274830 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Wan, Q | - |
dc.contributor.author | Xia, J | - |
dc.contributor.author | Lu, W | - |
dc.contributor.author | Yang, J | - |
dc.contributor.author | Che, CM | - |
dc.date.accessioned | 2019-09-10T02:29:42Z | - |
dc.date.available | 2019-09-10T02:29:42Z | - |
dc.date.issued | 2019 | - |
dc.identifier.citation | Journal of the American Chemical Society, 2019, v. 141 n. 29, p. 11572-11582 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10722/274830 | - |
dc.description.abstract | Metallophilic interactions in d10–d10(AuI–AuI)/d8–d8(PtII–PtII, RhI–RhI, IrI–IrI) complexes have been widely studied for decades, and metal–metal (M–M) bonding character has been revealed in both the ground and excited states. These M–M closed-shell interactions are appealing driving forces for the self-assembly of supramolecular/polymeric systems, providing luminescent properties distinctly different from those of the corresponding monomer. However, reports on attractive interactions between two AuIII complex cations are scarce in the literature. Herein is described a series of pincer-type cationic AuIII complexes with different auxiliary ligands, among which the AuIII–allenylidene complex displays a close Au–Au contact of 3.367 Å between neighboring molecules in its X-ray crystal structure; AuIII–isocyanide complexes show a broad red-shifted absorption band and prominent phosphorescence upon aggregation that was influenced by an attractive AuIII–AuIII bonding interaction in the excited state; and AuIII–acetylene complexes can undergo living supramolecular polymerization upon varying the counteranion. The nature of the emissive excited state(s) of the AuIII aggregates is assigned to a mixture of major 3[π–π*] and minor 3LMMCT (ligand-to-metal–metal charge transfer) states based on combined spectroscopic and DFT/TDDFT studies. The morphology of the AuIII aggregates is highly dependent on the concentration and nature of the counteranion. A qualitative model has been applied to account for the concentration- and counteranion-dependent kinetics of the supramolecular polymerization process. | - |
dc.language | eng | - |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | - |
dc.relation.ispartof | Journal of the American Chemical Society | - |
dc.rights | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.9b04007 | - |
dc.subject | Platinum | - |
dc.subject | Phosphorescence | - |
dc.subject | Ligands | - |
dc.title | Kinetically Controlled Self-assembly Of Phosphorescent Auiii Aggregates And Ligand-to-metal–metal Charge Transfer Excited State: A Combined Spectroscopic And DFT/TDDFT Study | - |
dc.type | Article | - |
dc.identifier.email | Yang, J: juny@hku.hk | - |
dc.identifier.email | Che, CM: chemhead@hku.hk | - |
dc.identifier.authority | Yang, J=rp02186 | - |
dc.identifier.authority | Che, CM=rp00670 | - |
dc.description.nature | postprint | - |
dc.identifier.doi | 10.1021/jacs.9b04007 | - |
dc.identifier.pmid | 31259541 | - |
dc.identifier.scopus | eid_2-s2.0-85070485325 | - |
dc.identifier.hkuros | 304692 | - |
dc.identifier.volume | 141 | - |
dc.identifier.issue | 29 | - |
dc.identifier.spage | 11572 | - |
dc.identifier.epage | 11582 | - |
dc.identifier.isi | WOS:000477787400033 | - |
dc.publisher.place | United States | - |
dc.identifier.issnl | 0002-7863 | - |