000131076 001__ 131076
000131076 005__ 20240205173707.0
000131076 0247_ $$2doi$$a10.1021/om800845c
000131076 0248_ $$2sideral$$a114340
000131076 037__ $$aART-2009-114340
000131076 041__ $$aeng
000131076 100__ $$aDiez, Alvaro
000131076 245__ $$aSynthesis and Luminescence of Cyclometalated Compounds with Nitrile and Isocyanide Ligands
000131076 260__ $$c2009
000131076 5060_ $$aAccess copy available to the general public$$fUnrestricted
000131076 5203_ $$aMononuclear cationic cyclometalated palladium complexes [Pd(C∧N)(NCMe)2]ClO4 [C∧N = benzoquinolinate (bzq) 1, 2-phenylpyridinate (ppy) 2], analogous to the previously described platinum complexes [Pt(C∧N)(NCMe)2]ClO4 [C∧N = bzq 3, ppy 4], and the isocyanide platinum benzoquinolinate [Pt(bzq)(CNR)2]X (R = tert-butyl (t-Bu, 5), 2,6-dimethylphenyl (Xyl, 6), 2-naphthyl (2-Np, 7); X = ClO4−a, PF6−b) have been prepared and characterized. The solid-state structures of the cation [Pt(C∧N)(CN-Xyl)2]+ with different counteranions (6a and 6b) were found to be different in terms of packing, although in both cases they were dominated by π−π intermolecular interactions. The influence of the counteranion in the UV−vis spectra, both in solution and in the solid state of 5−7, is negligible. Time-dependent density-functional theory calculations on cation [Pt(C∧N)(CN-Xyl)2]+ (6+) have been performed, suggesting that the lowest absorption is 1IL in nature mixed with some 1MLCT character. Acetonitrile platinum complexes (3, 4) are photoluminescent at low temperature (77 K) and at room temperature, whereas analogous palladium complexes (1, 2) are emissive only at 77 K (solid-state and glassy acetonitrile). Isocyanide derivatives 5−7 are intensely luminescent in all media. The emissions are assigned to ligand-centered fluorescence, to mixed 3LC/3MLCT phosphorescence, or to excimeric (or ground-state) 3ππ* or 3MMLCT [σ*(M)→π*(C∧N)] transitions depending on the medium and the excitation wavelength. The effect of the counteranion in governing the degree of aggregation and the extent of the interactions seem to be relatively important, especially in a rigid medium, with the smaller ClO4− inducing a more excimeric character. The tendency to form π−π excimers and/or Pt···Pt oligomerization follows the order CN-2-Np > CN-t-Bu > CN-Xyl and ClO4− > PF6−.
000131076 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2008-06669-C02-01-BQU$$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2008-06669-C02-02-BQU$$9info:eu-repo/grantAgreement/ES/MEC/CTQ2005-06807-BQU
000131076 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000131076 590__ $$a4.204$$b2009
000131076 591__ $$aCHEMISTRY, ORGANIC$$b9 / 57 = 0.158$$c2009$$dQ1$$eT1
000131076 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b4 / 44 = 0.091$$c2009$$dQ1$$eT1
000131076 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000131076 700__ $$0(orcid)0000-0003-1374-5880$$aFornies, Juan$$uUniversidad de Zaragoza
000131076 700__ $$0(orcid)0000-0003-1812-3175$$aFuertes, Sara
000131076 700__ $$aLalinde, Elena
000131076 700__ $$aLarraz, Carmen
000131076 700__ $$0(orcid)0000-0003-4500-1974$$aLopez, Jose A.$$uUniversidad de Zaragoza
000131076 700__ $$0(orcid)0000-0002-4808-574X$$aMartin, Antonio
000131076 700__ $$aMoreno, M. Teresa
000131076 700__ $$0(orcid)0000-0002-0257-0483$$aSicilia, Violeta$$uUniversidad de Zaragoza
000131076 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000131076 773__ $$g28, 6 (2009), 1705-1718$$pOrganometallics$$tOrganometallics$$x0276-7333
000131076 8564_ $$s1977862$$uhttps://zaguan.unizar.es/record/131076/files/texto_completo.pdf$$yPostprint
000131076 8564_ $$s794553$$uhttps://zaguan.unizar.es/record/131076/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000131076 909CO $$ooai:zaguan.unizar.es:131076$$particulos$$pdriver
000131076 951__ $$a2024-02-05-15:03:01
000131076 980__ $$aARTICLE