000127101 001__ 127101
000127101 005__ 20241125101146.0
000127101 0247_ $$2doi$$a10.1021/acs.inorgchem.3c00601
000127101 0248_ $$2sideral$$a134514
000127101 037__ $$aART-2023-134514
000127101 041__ $$aeng
000127101 100__ $$aDalmau, D.
000127101 245__ $$aFluorescence amplification of unsaturated oxazolones using palladium: photophysical and computational studies
000127101 260__ $$c2023
000127101 5060_ $$aAccess copy available to the general public$$fUnrestricted
000127101 5203_ $$aWeakly fluorescent (Z)-4-arylidene-5-(4H)-oxazolones (1), ΦPL < 0.1%, containing a variety of conjugated aromatic fragments and/or charged arylidene moieties, have been orthopalladated by reaction with Pd(OAc)2. The resulting dinuclear complexes (2) have the oxazolone ligands bonded as a C^N-chelate, restricting intramolecular motions involving the oxazolone. From 2, a variety of mononuclear derivatives, such as [Pd(C^N-oxazolone)(O2CCF3)(py)] (3), [Pd(C^N-oxazolone)(py)2](ClO4) (4), [Pd(C^N-oxazolone)(Cl)(py)] (5), and [Pd(C^N-oxazolone)(X)(NHC)] (6, 7), have been prepared and fully characterized. Most of complexes 3–6 are strongly fluorescent in solution in the range of wavelengths from green to yellow, with values of ΦPL up to 28% (4h), which are among the highest values of quantum yield ever reported for organometallic Pd complexes with bidentate ligands. This means that the introduction of the Pd in the oxazolone scaffold produces in some cases an amplification of the fluorescence of several orders of magnitude from the free ligand 1 to complexes 3–6. Systematic variations of the substituents of the oxazolones and the ancillary ligands show that the wavelength of emission is tuned by the nature of the oxazolone, while the quantum yield is deeply influenced by the change of ligands. TD-DFT studies of complexes 3–6 show a direct correlation between the participation of the Pd orbitals in the HOMO and the loss of emission through non-radiative pathways. This model allows the understanding of the amplification of the fluorescence and the future rational design of new organopalladium systems with improved properties.
000127101 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2019-104379RB-C21$$9info:eu-repo/grantAgreement/ES/AEI/PID2019-106394GB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E07-23R$$9info:eu-repo/grantAgreement/ES/DGA/E17-23R
000127101 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000127101 590__ $$a4.3$$b2023
000127101 592__ $$a0.928$$b2023
000127101 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b8 / 44 = 0.182$$c2023$$dQ1$$eT1
000127101 593__ $$aChemistry (miscellaneous)$$c2023$$dQ1
000127101 593__ $$aPhysical and Theoretical Chemistry$$c2023$$dQ1
000127101 593__ $$aInorganic Chemistry$$c2023$$dQ1
000127101 594__ $$a7.6$$b2023
000127101 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000127101 700__ $$0(orcid)0000-0001-9522-5840$$aCrespo, O.$$uUniversidad de Zaragoza
000127101 700__ $$aMatxain, J. M.
000127101 700__ $$0(orcid)0000-0001-9779-5820$$aUrriolabeitia, E. P.
000127101 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000127101 773__ $$g62, 25 (2023), 9792-9806$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000127101 8564_ $$s4871129$$uhttps://zaguan.unizar.es/record/127101/files/texto_completo.pdf$$yVersión publicada
000127101 8564_ $$s3167252$$uhttps://zaguan.unizar.es/record/127101/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000127101 909CO $$ooai:zaguan.unizar.es:127101$$particulos$$pdriver
000127101 951__ $$a2024-11-22-12:04:43
000127101 980__ $$aARTICLE