Synthesis, photophysical and theoretical studies of luminescent silver(I)-copper(I) alkynyl-diphosphine complexes. 2010

Igor O Koshevoy, and Antti J Karttunen, and Yi-Chih Lin, and Chao-Chen Lin, and Pi-Tai Chou, and Sergey P Tunik, and Matti Haukka, and Tapani A Pakkanen
University of Joensuu, Joensuu, 80101, Finland. igor.koshevoy@joensuu.fi

The novel heterometallic aggregates [Ag(8)Cu(2)(C(2)C(6)H(4)X)(6)(PPh(2)C(6)H(4)PPh(2))(6)][PF(6)](4) (X = H, 1; OMe, 2; NMe(2), 3) were prepared by the self-assembly reactions starting from simple precursors. These compounds consist of the central [Ag(6)Cu(2)(C(2)C(6)H(4)X)(6)](2+) clusters capped by two tripodal fragments [Ag(diphosphine)(3)](+). The solid state structures of complexes 1 and 3 have been determined by X-ray crystallographic studies, and NMR spectroscopy confirmed that the compounds remain intact in solution. In solution such as CH(3)CN, complexes 1-3 show a weak to moderate room-temperature phosphorescence in the blue region with a maximum quantum yield of 0.038 (2), while strong phosphorescence was recorded in the solid film of with a quantum yield of 0.26. Photophysical experiments revealed a relatively small effect of luminescence quenching by O(2) for 1, but more prominent quenching for 2 and 3 in solution. Computational approaches are in good agreement with the experimental data, supporting the proposed structural motif, and provide an additional insight into the electronic properties of these compounds to rationalize the different behavior of 1 compared to 2 and 3.

UI MeSH Term Description Entries
D008958 Models, Molecular Models used experimentally or theoretically to study molecular shape, electronic properties, or interactions; includes analogous molecules, computer-generated graphics, and mechanical structures. Molecular Models,Model, Molecular,Molecular Model
D009942 Organometallic Compounds A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed) Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D010720 Phosphines Inorganic or organic compounds derived from phosphine (PH3) by the replacement of H atoms. (From Grant & Hackh's Chemical Dictionary, 5th ed)
D010777 Photochemistry A branch of physical chemistry which studies chemical reactions, isomerization and physical behavior that may occur under the influence of visible and/or ultraviolet light. Photochemistries
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D003198 Computer Simulation Computer-based representation of physical systems and phenomena such as chemical processes. Computational Modeling,Computational Modelling,Computer Models,In silico Modeling,In silico Models,In silico Simulation,Models, Computer,Computerized Models,Computer Model,Computer Simulations,Computerized Model,In silico Model,Model, Computer,Model, Computerized,Model, In silico,Modeling, Computational,Modeling, In silico,Modelling, Computational,Simulation, Computer,Simulation, In silico,Simulations, Computer
D003300 Copper A heavy metal trace element with the atomic symbol Cu, atomic number 29, and atomic weight 63.55. Copper-63,Copper 63
D000480 Alkynes Hydrocarbons with at least one triple bond in the linear portion, of the general formula Cn-H2n-2. Acetylenic Compounds,Alkyne,Acetylenes
D012834 Silver An element with the atomic symbol Ag, atomic number 47, and atomic weight 107.87. It is a soft metal that is used medically in surgical instruments, dental prostheses, and alloys. Long-continued use of silver salts can lead to a form of poisoning known as ARGYRIA.
D013237 Stereoisomerism The phenomenon whereby compounds whose molecules have the same number and kind of atoms and the same atomic arrangement, but differ in their spatial relationships. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 5th ed) Molecular Stereochemistry,Stereoisomers,Stereochemistry, Molecular,Stereoisomer

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