000148561 001__ 148561
000148561 005__ 20250120165542.0
000148561 0247_ $$2doi$$a10.1021/acs.inorgchem.1c01470
000148561 0248_ $$2sideral$$a127065
000148561 037__ $$aART-2021-127065
000148561 041__ $$aeng
000148561 100__ $$0(orcid)0000-0002-0257-0483$$aSicilia, V.$$uUniversidad de Zaragoza
000148561 245__ $$aChameleonic Photo- and Mechanoluminescence in Pyrazolate-Bridged NHC Cyclometalated Platinum Complexes
000148561 260__ $$c2021
000148561 5060_ $$aAccess copy available to the general public$$fUnrestricted
000148561 5203_ $$aDFT investigations on the ground (GS) and the first triplet (T1) excited state potential energy surfaces (PES) were performed on a new series of platinum-butterfly complexes, [{Pt(C¿C*)(µ-Rpz)}2] (Rpz: pz, 1; 4-Mepz, 2; 3, 5-dmpz, 3; 3, 5-dppz, 4), containing a cyclometalated NHC in their wings. The geometries of two close-lying local minima corresponding to butterfly spread conformers, 1s-4s, and butterfly folded ones, 1f-4f, with long and short Pt-Pt separations, respectively, were optimized in the GS and T1 PES. A comparison of the GS and T1 energy profiles revealed that an opposite trend is obtained in the relative stability of folded and spread conformers, the latter being more stabilized in their GS. Small ¿G (s/f) along with small-energy barriers in the GS support the coexistence of both kinds of conformers, which influence the photo- and mechanoluminescence of these complexes. In 5 wt % doped PMMA films in the air, these complexes exhibit intense sky-blue emissions (PLQY: 72.0-85.9%) upon excitation at ¿ = 380 nm arising from 3IL/MLCT excited states, corresponding to the predominant 1s-4s conformers. Upon excitation at longer wavelengths (up to 450 nm), the minor 1f-4f conformers afford a blue emission as well, with PLQY still significant (40%-60%). In the solid state, the as-prepared powder of 4 exhibits a greenish-blue emission with QY ~29%, mainly due to 3IL/3MLCT excited states of butterfly spread molecules, 4s. Mechanical grinding resulted in an enhanced and yellowish-green emission (QY ~51%) due to the 3MMLCT excited states of butterfly folded molecules, 4f, in such a way that the mechanoluminescence has been associated with an intramolecular structural change induced by mechanical grinding.
000148561 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E17-20R$$9info:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00
000148561 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000148561 590__ $$a5.436$$b2021
000148561 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 46 = 0.109$$c2021$$dQ1$$eT1
000148561 592__ $$a1.121$$b2021
000148561 593__ $$aInorganic Chemistry$$c2021$$dQ1
000148561 593__ $$aChemistry (miscellaneous)$$c2021$$dQ1
000148561 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000148561 700__ $$0(orcid)0000-0002-0283-9307$$aArnal, L.$$uUniversidad de Zaragoza
000148561 700__ $$aEscudero, D.
000148561 700__ $$0(orcid)0000-0003-1812-3175$$aFuertes, S.
000148561 700__ $$0(orcid)0000-0002-4808-574X$$aMartin, A.
000148561 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000148561 773__ $$g60, 16 (2021), 12274-12284$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000148561 8564_ $$s4468380$$uhttps://zaguan.unizar.es/record/148561/files/texto_completo.pdf$$yVersión publicada
000148561 8564_ $$s2973513$$uhttps://zaguan.unizar.es/record/148561/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000148561 909CO $$ooai:zaguan.unizar.es:148561$$particulos$$pdriver
000148561 951__ $$a2025-01-20-14:53:08
000148561 980__ $$aARTICLE