000135729 001__ 135729
000135729 005__ 20260217205511.0
000135729 0247_ $$2doi$$a10.1039/d4dt00730a
000135729 0248_ $$2sideral$$a138759
000135729 037__ $$aART-2024-138759
000135729 041__ $$aeng
000135729 100__ $$aDumitras, Darius
000135729 245__ $$aOrthopalladated imidazolones and thiazolones: synthesis, photophysical properties and photochemical reactivity
000135729 260__ $$c2024
000135729 5060_ $$aAccess copy available to the general public$$fUnrestricted
000135729 5203_ $$aThe reaction of Pd(OAc)2 with (Z)-5-arylidene-4-(4H)-imidazolones (2a–e) and (Z)-4-arylidene-5(4H)-thiazolones (3a–e) in trifluoroacetic acid results in the corresponding orthopalladated dinuclear complexes (4a–e, imidazolones; 11a–d, thiazolones) with trifluoroacetate bridges through regioselective C–H activation at the ortho position of the 4-arylidene group. Compound 4e, which contains an imidazolone substituted at 2- and 4-positions of the arylidene ring with methoxide groups and exhibits strong push–pull charge transfer, is an excellent precursor for the synthesis of fluorescent complexes with green yellowish emission and remarkable quantum yields. Breaking the bridging system with pyridine yields the mononuclear complex 5e (ΦF = 5%), while metathesis of trifluoroacetate ligands with chloride leads to the dinuclear complex 6e, also a precursor of fluorescent complexes by breaking the chloride bridging system with pyridine (7e, ΦF = 7%), or by substitution of chloride ligands with pyridine (8e, ΦF = 15%) or acetylacetonate (9e, ΦF = 2%). In addition to notable photophysical properties, dinuclear complexes 4 and 11 also exhibit significant photochemical reactivity. Thus, irradiation of orthopalladates 4a–c and 11a–c in CH2Cl2 with blue light (465 nm) proceeds via [2 + 2] photocycloaddition of the C[double bond, length as m-dash]C double bonds of imidazolone and thiazolone ligands, yielding the corresponding cyclobutane-bridging diaminotruxillic derivatives 10a–c and 12a–c, respectively.
000135729 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2019-106394GB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E17-23R
000135729 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttps://creativecommons.org/licenses/by-nc/4.0/deed.es
000135729 590__ $$a3.3$$b2024
000135729 592__ $$a0.653$$b2024
000135729 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b10 / 43 = 0.233$$c2024$$dQ1$$eT1
000135729 593__ $$aInorganic Chemistry$$c2024$$dQ2
000135729 594__ $$a6.0$$b2024
000135729 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000135729 700__ $$aDalmau, David
000135729 700__ $$aGarcía-Orduña, Pilar
000135729 700__ $$aPop, Alexandra
000135729 700__ $$aSilvestru, Anca
000135729 700__ $$0(orcid)0000-0001-9779-5820$$aUrriolabeitia, Esteban P.
000135729 773__ $$g53, 21 (2024), 8948-8957$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000135729 8564_ $$s1277816$$uhttps://zaguan.unizar.es/record/135729/files/texto_completo.pdf$$yVersión publicada
000135729 8564_ $$s2734657$$uhttps://zaguan.unizar.es/record/135729/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000135729 909CO $$ooai:zaguan.unizar.es:135729$$particulos$$pdriver
000135729 951__ $$a2026-02-17-20:25:18
000135729 980__ $$aARTICLE