title: Luminescence Solvato- and Vapochromism of Alkynyl-Phosphine Copper Clusters
metadata.name: dc.contributor.author
metadata.value: Krytchankou, Ilya S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Koshevoy, Igor O
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Gurzhiy, Vladislav V
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Pomogaev, Vladimir A
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Tunik, Sergey P
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-05-06T14:42:04Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-05-06T14:42:04Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015-09-08
metadata.lang: -
metadata.name: dc.identifier
metadata.value: 10.1021/acs.inorgchem.5b00239
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 0020-1669
metadata.lang: -
metadata.name: dc.identifier.other
metadata.value: 10.1021/acs.inorgchem.5b00239
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/2253
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: The reaction of [Cu(NCMe)4][PF6] with aromatic acetylenes HC2R and triphosphine 1,1,1-tris(diphenylphosphino)methane in the presence of NEt3 results in the formation of hexanuclear Cu(I) clusters with the general formula [Cu6(C2R)4{(PPh2)3CH}2][PF6]2 (R = 4-X-C6H4 (1-5) and C5H4N (6); X = NMe2 (1), OMe (2), H (3), Ph (4), CF3 (5)). The structural motif of the complexes studied consists of a Cu6 metal core supported by two phosphine ligands and stabilized by σ- and π-coordination of the alkynyl fragments (together with coordination of pyridine nitrogen atoms in cluster 6). The solid state structures of complexes 2-6 were determined by single crystal XRD analysis. The structures of the complexes in solution were elucidated by (1)H, (31)P, (1)H-(1)H COSY NMR spectroscopy, and ESI mass spectrometry. Clusters 1-6 exhibit moderately strong phosphorescence in the solid state with quantum yields up to 17%. Complexes 1-5 were found to form solvates (acetone, acetonitrile) in the solid state. The coordination of loosely bound solvent molecules strongly affects emission characteristics and leads to solvato- and vapochromic behavior of the clusters. Thus, solvent-free and acetonitrile solvated forms of 3 demonstrate contrasting emission in orange (615 nm) and blue (475 nm) regions, respectively. The computational studies show that alkynyl-centered IL transitions mixed with those of MLCT between the Cu6 metal core and the ligand environment play a dominant role in the formation of excited states and can be considerably modulated by weakly coordinating solvent molecules leading to luminescence vapochromism.
metadata.lang: en_GB
metadata.name: dc.description.sponsorship
metadata.value: This research has been supported by St. Petersburg State University Research Grant 0.37.169.2014, and Russian Foundation for Basic Research Grants 13-03-00970, 14-03-32077, and 13-03-12411. Academy of Finland (Grant 268993/2013, I.O.K), University of Eastern Finland (strategic funding—Russian–Finnish collaborative project), is also gratefully acknowledged. The work was carried out using equipment of the Analytical Center of Nano- and Biotechnologies of SPbSPU with financial support of the Ministry of Education and Science of Russian Federation; Centers for Magnetic Resonance, X-ray Diffraction Studies, Chemical Analysis and Materials Research, Optical and Laser Materials Research; and Computer Center of St. Petersburg State University.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.publisher
metadata.value: American Chemichal Society
metadata.lang: en_GB
metadata.name: dc.relation.ispartofseries
metadata.value: Inorganic Chemistry;V. 54. Issue 17
metadata.lang: -
metadata.name: dc.title
metadata.value: Luminescence Solvato- and Vapochromism of Alkynyl-Phosphine Copper Clusters
metadata.lang: en_GB
metadata.name: dc.type
metadata.value: Article
metadata.lang: en_GB
resources.filename: 2015_InorgChem_Ilya.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/2253/1/2015_InorgChem_Ilya.pdf
resources.format: Adobe PDF
resources.size: 2,74 MB