000162569 001__ 162569
000162569 005__ 20251017144613.0
000162569 0247_ $$2doi$$a10.1021/acs.inorgchem.5c02714
000162569 0248_ $$2sideral$$a145121
000162569 037__ $$aART-2025-145121
000162569 041__ $$aeng
000162569 100__ $$aBerbés Martínez, Roberto
000162569 245__ $$aAlkynyl-Gold Carbazole Hybrids: Luminescence and Functionalization via iClick Reactions
000162569 260__ $$c2025
000162569 5060_ $$aAccess copy available to the general public$$fUnrestricted
000162569 5203_ $$aA series of structurally diverse gold(I) complexes bearing the 9-(4-ethynylphenyl)-9H-carbazole chromophore were synthesized, featuring mononuclear, dinuclear, tricoordinated, and supramolecular architectures. Their formation involved either alkynylation reactions or the reaction of polymeric alkynyl species [Au(C≡CR)]n with auxiliary ligands. Notably, an equilibrium between bimetallic and tricoordinated species was observed when diphosphine ligands were employed, highlighting the dynamic nature of these systems. This equilibrium was found to be solvent-dependent, with the pure tricoordinated complex isolable in a nonpolar solvent. The triazole complexes were synthesized via iClick chemistry by reacting the carbazole-functionalized alkyne with azide-phosphine gold(I) precursors. Structural analysis confirmed hydrogen-bonding frameworks and the absence of π–π stacking. Photophysical studies demonstrated intense solid-state phosphorescence, with blue-green luminescence markedly enhanced at 77 K. At room temperature, emission broadened (450–600 nm) and red-shifted compared to the free ligand, indicating a synergistic contribution of carbazole-centered (3IL) and intramolecular charge transfer (ICT) transitions. This metal-tuned photophysical behavior underscores the potential of these gold complexes in luminescent materials. This charge transfer, occurring from the carbazole to the ligand system is mediated by the phenyl ring and modulated by metal coordination. TD-DFT calculations were performed to analyze the molecular orbitals involved in both the absorption (S0 → S1) and emission (T1 → S0) transitions of the complex 1, indicating that the emission is predominantly of intraligand character, although coordination to the Au(I) center induces slight modifications in the energy levels and transition intensities.
000162569 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E07-23R$$9info:eu-repo/grantAgreement/ES/MICINN AEI/PID2022-136861NB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2022-140159NA-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2023-147471NB-I00
000162569 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000162569 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000162569 700__ $$0(orcid)0000-0002-0769-7168$$aAlegre-Requena, Juan V.
000162569 700__ $$0(orcid)0000-0002-5244-9569$$aPérez Herrera, Raquel
000162569 700__ $$0(orcid)0000-0003-0553-0695$$aGimeno Floría, M. Concepción
000162569 773__ $$g64, 34 (2025), 17399-17408$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000162569 8564_ $$s3723686$$uhttps://zaguan.unizar.es/record/162569/files/texto_completo.pdf$$yVersión publicada
000162569 8564_ $$s3092491$$uhttps://zaguan.unizar.es/record/162569/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000162569 909CO $$ooai:zaguan.unizar.es:162569$$particulos$$pdriver
000162569 951__ $$a2025-10-17-14:18:11
000162569 980__ $$aARTICLE