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

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dc.contributor.authorSaldías, Marianela
dc.contributor.authorManzur, Jorge
dc.contributor.authorPalacios, Rodrigo E.
dc.contributor.authorGómez, María L.
dc.contributor.authorFuente, Julio De La
dc.contributor.authorGünther, Germán
dc.contributor.authorPizarro, Nancy
dc.contributor.authorVega, Andrés
dc.date.accessioned2024-09-24T15:27:48Z
dc.date.available2024-09-24T15:27:48Z
dc.date.issued2017
dc.descriptionIndexación: Scopus
dc.description.abstractLithium 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 metal-centered 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 3MLCT 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 and states. © 2017 The Royal Society of Chemistry.
dc.description.urihttps://pubs.rsc.org/en/content/articlelanding/2017/dt/c6dt04158b
dc.identifier.citationDalton Transactions Volume 46, Issue 5, Pages 1567 - 15762017
dc.identifier.doi10.1039/c6dt04158b
dc.identifier.issn1477-9226
dc.identifier.urihttps://repositorio.unab.cl/handle/ria/60445
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.rights.licenseAtribución 3.0 Chile CC BY 3.0 CL Deed
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/cl/deed.es
dc.titleThe 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
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