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Thermochromic luminescence of copper iodide clusters: the case of phosphine ligands.

hal.structure.identifierLaboratoire de physique de la matière condensée [LPMC]
dc.contributor.authorPERRUCHAS, Sandrine
hal.structure.identifierLaboratoire de physique de la matière condensée [LPMC]
dc.contributor.authorTARD, Cédric
hal.structure.identifierLaboratoire Hétéroéléments et Coordination [DCPH]
dc.contributor.authorLE GOFF, X.
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorFARGUES, Alexandre
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorGARCIA, Alain
hal.structure.identifierInstitut des Sciences Chimiques de Rennes [ISCR]
dc.contributor.authorKAHLAL, Samia
hal.structure.identifierInstitut des Sciences Chimiques de Rennes [ISCR]
hal.structure.identifierUniversité européenne de Bretagne - European University of Brittany [UEB]
dc.contributor.authorSAILLARD, Jean-Yves
hal.structure.identifierLaboratoire de physique de la matière condensée [LPMC]
dc.contributor.authorGACOIN, Thierry
hal.structure.identifierLaboratoire de physique de la matière condensée [LPMC]
dc.contributor.authorBOILOT, Jean-Pierre
dc.date.issued2011
dc.identifier.issn0020-1669
dc.description.abstractEnThree copper(I) iodide clusters coordinated by different phosphine ligands formulated [Cu(4)I(4)(PPh(3))(4)] (1), [Cu(4)I(4)(Pcpent(3))(4)] (2), and [Cu(4)I(4)(PPh(2)Pr)(4)] (3) (PPh(3) = triphenylphosphine, Pcpent(3) = tricyclopentylphosphine, and PPh(2)Pr = diphenylpropylphosphine) have been synthesized and characterized by (1)H and (31)P NMR, elemental analysis and single crystal X-ray diffraction analysis. They crystallize in different space groups, namely, monoclinic P21/c, cubic Pa3̅, and tetragonal I4̅2m for 1, 2, and 3, respectively. The photoluminescence properties of clusters 1 and 3 show reversible luminescence thermochromism with two highly intense emission bands whose intensities are temperature dependent. In accordance to Density Functional Theory (DFT) calculations, these two emission bands have been attributed to two different transitions, a cluster centered (CC) one and a mixed XMCT/XLCT one. Cluster 2 does not exhibit luminescence variation in temperature because of the lack of the latter transition. The absorption spectra of the three clusters have been also rationalized by time dependent DFT (TDDFT) calculations. A simplified model is suggested to represent the luminescence thermochromism attributed to the two different excited states in thermal equilibrium. In contrast with the pyridine derivatives, similar excitation profiles and low activation energy for these phosphine-based clusters reflect high coupling of the two emissive states. The effect of the Cu-Cu interactions on the emission properties of these clusters is also discussed. Especially, cluster 3 with long Cu-Cu contacts exhibits a controlled thermochromic luminescence which is to our knowledge, unknown for this family of copper iodide clusters. These phosphine-based clusters appear particularly interesting for the synthesis of original emissive materials.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enThermochromic luminescence
dc.subject.enIodide
dc.subject.enCopper
dc.subject.enLigands
dc.subject.enPhosphine
dc.title.enThermochromic luminescence of copper iodide clusters: the case of phosphine ligands.
dc.typeArticle de revue
dc.identifier.doi10.1021/ic201128a
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page10682-10692
bordeaux.volume50
bordeaux.issue21
bordeaux.peerReviewedoui
hal.identifierhal-00646861
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00646861v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic%20Chemistry&rft.date=2011&rft.volume=50&rft.issue=21&rft.spage=10682-10692&rft.epage=10682-10692&rft.eissn=0020-1669&rft.issn=0020-1669&rft.au=PERRUCHAS,%20Sandrine&TARD,%20C%C3%A9dric&LE%20GOFF,%20X.&FARGUES,%20Alexandre&GARCIA,%20Alain&rft.genre=article


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