000145634 001__ 145634
000145634 005__ 20241114112316.0
000145634 0247_ $$2doi$$a10.3390/inorganics12100271
000145634 0248_ $$2sideral$$a140555
000145634 037__ $$aART-2024-140555
000145634 041__ $$aeng
000145634 100__ $$aMartínez, Miguel
000145634 245__ $$aDifferent Patterns of Pd-Promoted C-H Bond Activation in (Z)-4-Hetarylidene-5(4H)-oxazolones and Consequences in Photophysical Properties
000145634 260__ $$c2024
000145634 5060_ $$aAccess copy available to the general public$$fUnrestricted
000145634 5203_ $$aThis work aims to amplify the fluorescence of (Z)-4-hetarylidene-5(4H)-oxazolones 1 by suppression of the hula-twist non-radiative deactivation pathway by C^N-orthopalladation of the 4-hetarylidene ring. Different (Z)-4-hetarylidene-2-phenyl-5(4H)-oxazolones, 1a–1c, prepared by the Erlenmeyer–Plöchl method, have been studied. The orthopalladation of (Z)-2-phenyl-4-(5-thiazolylmethylene)-5(4H)-oxazolone (1a) takes place by C-H bond activation of the H4 of the heterocycle and C^N-chelation, giving the dinuclear trifluoroacetate derivative 2a. By further metathesis of bridging ligands in 2a, complexes containing the orthometalated oxazolone and a variety of ligands 3a–5a, were prepared. The study of the photophysical properties of 1a–5a shows that the bonding of the Pd metal to the 4-hetaryliden-5(4H)-oxazolone does not promote, in these cases, an increase in fluorescence. Interestingly, the orthopalladation of (Z)-2-phenyl-4-(4-thiazolylmethylene)-5(4H)-oxazolone (1b) gives orthopalladated 2b, where the incorporation of the Pd to the oxazolone takes place by C-H bond activation of the ortho-H2 of the 2-phenyl group, ring opening of the oxazolone heterocycle and simultaneous N,N-bonding of the N atoms of the thiazole ring and the generated benzamide fragment. This N^N^C-tridentate dianionic bonding mode is obtained for the first time in oxazolones. Despite a similar lock of the hula-twist deactivation, 2b does not show fluorescence.
000145634 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E07-23R$$9info:eu-repo/grantAgreement/ES/DGA/E17-23R$$9info:eu-repo/grantAgreement/ES/MICINN AEI/PID2022-136861NB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2019-106394GB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00
000145634 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000145634 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000145634 700__ $$aDalmau, David
000145634 700__ $$0(orcid)0000-0001-9522-5840$$aCrespo, Olga$$uUniversidad de Zaragoza
000145634 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000145634 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando
000145634 700__ $$0(orcid)0000-0002-4808-574X$$aMartín, Antonio
000145634 700__ $$0(orcid)0000-0001-9779-5820$$aUrriolabeitia, Esteban P.
000145634 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000145634 773__ $$g12, 10 (2024), 271 [16 pp.]$$tInorganics$$x2304-6740
000145634 8564_ $$s2252442$$uhttps://zaguan.unizar.es/record/145634/files/texto_completo.pdf$$yVersión publicada
000145634 8564_ $$s2737805$$uhttps://zaguan.unizar.es/record/145634/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000145634 909CO $$ooai:zaguan.unizar.es:145634$$particulos$$pdriver
000145634 951__ $$a2024-11-14-10:18:22
000145634 980__ $$aARTICLE