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dc.contributor.author
Saldías, Marianela
dc.contributor.author
Manzur, Jorge
dc.contributor.author
Palacios, Rodrigo Emiliano
dc.contributor.author
Gomez, María Lorena
dc.contributor.author
de la Fuente, Julio
dc.contributor.author
Günther, Germán
dc.contributor.author
Pizarro, Nancy
dc.contributor.author
Vega, Andrés
dc.date.available
2017-09-20T19:07:06Z
dc.date.issued
2017-01
dc.identifier.citation
Saldías, Marianela; Manzur, Jorge; Palacios, Rodrigo Emiliano; Gomez, María Lorena; de la Fuente, Julio; et al.; The binuclear dual emitter [Br(CO)3Re(P⋯N)(N⋯P)Re(CO)3Br] (P⋯N): 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine, a new bridging P,N-bidentate ligand resulting from the ring opening of tetrahydrofuran; Royal Society of Chemistry; Dalton Transactions; 46; 5; 1-2017; 1567-1576
dc.identifier.issn
1477-9226
dc.identifier.uri
http://hdl.handle.net/11336/24722
dc.description.abstract
Lithium diphenylphosphide unexpectedly provokes the ring-opening of tetrahydrofuran (THF) and by reaction with 3,6-dichloropyridazine leads to the formation of the ligand 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine (P⋯N), which was isolated. The reaction of this ligand with the (Re(CO)3(THF)Br)2 dimer yields the novel complex [Br(CO)3Re(μ-3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine)2Re (CO)3Br] (BrRe(P⋯N)(N⋯P)ReBr), which was crystallized in the form of a chloroform solvate, (C46H40Br2Cl2N4O8P2Re2)·(CHCl3). The monoclinic crystal (P21/n) displays a bimetallic cage structure with a symmetry inversion centre in the middle of the rhenium to rhenium line. The molecule shows two oxidation signals occurring at +1.50 V and +1.76 V which were assigned to the ReI /ReII and ReII/ReIII metalcentered couples, respectively, while signals observed at −1.38 V and −1.68 V were assigned to ligand centered reductions. Experimental and DFT/TDDFT results indicate that the UV-Vis absorption maximum of BrRe(P⋯N)(N⋯P)ReBr occurring near 380 nm displays a metal to ligand charge transfer (MLCT) character, which is consistent with CV results. Upon excitation at this wavelength, a weak emission (Φem < 1 × 10−3 ) is observed around 580 nm (in dichloromethane) which decays with two distinct lifetimes τ1 and τ2 of 24 and 4.7 ns, respectively. The prevalence of non-radiative deactivation pathways is consistent with efficient internal conversion induced by the high conformational flexibility of the P⋯N ligand’s long carbon chain. Measurements in a frozen solvent at 77 K, where vibrational deactivation is hindered, show intense emission associated with the 3 MLCT state. These results demonstrate that BrRe(P⋯N)(N⋯P)ReBr preserves the dual emitting nature previously reported for the mononuclear complex RePNBr, with emission associated with π* phenyl and π* pyridazine states.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Rhenium Complexes
dc.subject
Metal to Ligand Charge Transfer
dc.subject
Emission
dc.subject.classification
Otras Ciencias Químicas
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
The binuclear dual emitter [Br(CO)3Re(P⋯N)(N⋯P)Re(CO)3Br] (P⋯N): 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine, a new bridging P,N-bidentate ligand resulting from the ring opening of tetrahydrofuran
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-07-13T18:17:34Z
dc.journal.volume
46
dc.journal.number
5
dc.journal.pagination
1567-1576
dc.journal.pais
Reino Unido
dc.description.fil
Fil: Saldías, Marianela. Universidad Andres Bello; Chile
dc.description.fil
Fil: Manzur, Jorge. Universidad de Chile; Chile
dc.description.fil
Fil: Palacios, Rodrigo Emiliano. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil
Fil: Gomez, María Lorena. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
dc.description.fil
Fil: de la Fuente, Julio. Universidad de Chile; Chile
dc.description.fil
Fil: Günther, Germán. Universidad de Chile; Chile
dc.description.fil
Fil: Pizarro, Nancy. Universidad Andres Bello; Chile
dc.description.fil
Fil: Vega, Andrés. Universidad Andres Bello; Chile
dc.journal.title
Dalton Transactions
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1039/c6dt04158b
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C6DT04158B#!divAbstract


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