Synthesis and Photophysical Properties of Cyclometallated Pt(II) 1,2-Benzenedithiolate Complexes and Heterometallic Derivatives Obtained from the Addition of [Au(PCy3)]+ Units

Juliá Hernández, Fabio; Jones, Peter G.; González Herrero, Pablo

Publication:
Synthesis and Photophysical Properties of Cyclometallated Pt(II) 1,2-Benzenedithiolate Complexes and Heterometallic Derivatives Obtained from the Addition of [Au(PCy3)]+ Units

dc.contributor.author	Juliá Hernández, Fabio
dc.contributor.author	Jones, Peter G.
dc.contributor.author	González Herrero, Pablo
dc.contributor.department	Química Inorgánica
dc.date.accessioned	2024-02-07T08:19:24Z
dc.date.available	2024-02-07T08:19:24Z
dc.date.copyright	© 2012 American Chemical Society, after peer review and technical editing by the publisher.
dc.date.issued	2012-04-13
dc.description.abstract	The cyclometalated compounds [Pt(C^N)(HC^N)Cl] [HC^N = 2-phenylpyridine (Hppy; 1a), 1-(4-tert-butylphenyl)isoquinoline (Htbpiq; 1b)] react with 1,2-benzenedithiol, t-BuOK, and Bu4NCl in a 1:1:2:1 molar ratio in CH2Cl2/MeOH to give the complexes Bu4N[Pt(C^N)(bdt)] [bdt = 1,2-benzenedithiolate; C^N = ppy (Bu4N2a), tbpiq (Bu4N2b)]. In the absence of Bu4NCl, the same reactions afford solutions of K2a and K2b, which react with [AuCl(PCy3)] to give the neutral heterometallic derivatives [Pt(C^N)(bdt){Au(PCy3)}] [C^N = ppy (3a), tbpiq (3b)]. The cationic derivatives [Pt(C^N)(bdt){Au(PCy3)}2]ClO4 [C^N = ppy (4a), tbpiq (4b)] are obtained by reacting 3a and 3b with acetone solutions of [Au(OClO3)(PCy3)]. The crystal structures of 3b and 4b reveal the formation of short Pt···Au metallophilic contacts in the range 2.929–3.149 Å. Complexes 3b, 4a, and 4b undergo dynamic processes in solution that involve the migration of the [Au(PCy3)]+ units between the S atoms of the dithiolate. Complexes Bu4N2a and 2b display a moderately solvatochromic band in their electronic absorption spectra that can be ascribed to a transition of mixed ML′CT/LL′CT character (M= metal; L = bdt; L′ = C^N; CT = charge transfer), while their emissions are assignable to transitions of the same orbital parentage but from triplet excited states. The successive addition of [Au(PCy3)]+ units to the anions 2a and 2b results in an increase in the absorption and emission energies attributable to lower highest occupied molecular orbital energies. Additionally, the characteristics of the absorption and emission spectra of the heterometallic derivatives indicate a gradual loss of LL′CT character in the involved electronic transitions, with a concomitant increase of the L′C and ML′CT contributions.	es
dc.format	application/pdf	es
dc.format.extent	52
dc.identifier.citation	Inorganic Chemistry 2012, 51, 9, 5037–5049
dc.identifier.doi	https://doi.org/10.1021/ic202465k
dc.identifier.eissn	1520-510X
dc.identifier.issn	0020-1669
dc.identifier.uri	http://hdl.handle.net/10201/138778
dc.language	eng	es
dc.publisher	American Chemical Society
dc.relation	We thank Ministerio de Educación y Ciencia (Spain), FEDER (CTQ2007- 60808) and Fundación Séneca (04539/GERM/06) for financial support.	es
dc.relation.publisherversion	https://pubs.acs.org/doi/10.1021/ic202465k
dc.rights	info:eu-repo/semantics/openAccess	es
dc.rights	Attribution-NonCommercial-NoDerivatives 4.0 Internacional	*
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/	*
dc.subject	Absorption
dc.subject	Energy
dc.subject	Ligands
dc.subject	Organic polymers
dc.subject	Reaction products
dc.title	Synthesis and Photophysical Properties of Cyclometallated Pt(II) 1,2-Benzenedithiolate Complexes and Heterometallic Derivatives Obtained from the Addition of [Au(PCy3)]+ Units	es
dc.type	info:eu-repo/semantics/article	es
dc.type.version	info:eu-repo/semantics/acceptedVersion
dspace.entity.type	Publication	es
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