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dc.contributor.authorLasanta, Tania-
dc.contributor.authorLaguna, Antonio-
dc.identifierdoi: 10.1021/ja206845s-
dc.identifierissn: 0002-7863-
dc.identifiere-issn: 1520-5126-
dc.identifier.citationJournal of the American Chemical Society 133(41): 16358-16361 (2011)-
dc.description.abstractAiming at the development of new architectures within the context of the quest for strongly luminescent materials with tunable emission, we utilized the propensity of the robust bimetallic clusters [Au2Ag 2(RI/RII)4] (RI = 4-C6F4I, RII = 2-C6F 4I)for self-assembly through aurophilic interactions. With a de novo approach that combines the coordination and halogen-bonding potential of aromatic heteroperhalogenated ligands, we have generated a family of remarkably luminescent bimetallic materials that provide grounds to address the relevance, relative effects, and synergistic action of the two interactions in the underlying photophysics. By polymerizing the green-emitting (λ maxem = 540 nm) monomer [Au2Ag2R II 4(tfa)2]2- (tfa = trifluoroacetate) to a red-emitting (λmaxem = 660 nm) polymer [Au2Ag2RII 4(MeCN)2] n, we demonstrate herein that the degree of cluster association in these materials can be effectively and reversibly switched simply by applying mechanochemical and/or vapochemical stimuli in the solid state as well as by solvatochemistry in solution, the reactions being coincident with a dramatic switching of the intense, readily perceptible photoluminescence. We demonstrate that the key event in the related equilibrium is the evolution of a metastable yellow emitter (λmaxem = 580 nm) for which the structure determination in the case of the ligand RII revealed a dimeric nonsolvated topology [Au2Ag2RII 4]2. Taken together, these results reveal a two-stage scenario for the aurophilic-driven self-assembly of the bimetallic clusters [Au2Ag2(RI/RII)4]: (1) initial association of the green-emitting monomers to form metastable yellow-emitting dimers and desolvation followed by (2) resolvation of the dimers and their self-assembly to form a red-emitting linear architecture with delocalized frontier orbitals and a reduced energy gap. The green emission from [Au2Ag2RII 4(tfa)2] 2- (λmaxem = 540 nm) exceeds the highest energy observed for [Au2Ag2]-based structures to date, thereby expanding the spectral slice for emission from related structures beyond 140 nm, from the green region to the deep-red region. © 2011 American Chemical Society.-
dc.description.sponsorshipThis work was supported by Project D.G.I.(MEC)/FEDER (CTQ2010-20500-C02-02) and partially also by a Global COE Program, “The Global Education and Research Center for Bio-Environmental Chemistry”, from the Ministry of Education, Culture, Sports, Science and Technology, Japan. T.L. thanks MICINN for a grant. -
dc.publisherAmerican Chemical Society-
dc.titleMaking the golden connection: Reversible mechanochemical and vapochemical switching of luminescence from bimetallic gold-silver clusters associated through aurophilic interactions-
dc.description.versionPeer Reviewed-
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