TY - JOUR
T1 - Triphosphine-supported bimetallic Au-I-M-I (M = Ag, Cu) alkynyl clusters
AU - Krytchankou, Ilya S.
AU - Krupenya, Dmitry V.
AU - Karttunen, Antti J.
AU - Tunik, Sergey P.
AU - Pakkanen, Tapani A.
AU - Chou, Pi-Tai
AU - Koshevoy, Igor O.
PY - 2014
Y1 - 2014
N2 - The reactions of gold acetylides (AuC2R)(n) with triphosphine ligands PPh2(CH2)(n)-PPh-(CH2)(2)-PPh2 (n = 1, dpmp; 2, dpep) in the presence of M+ ions (M = Cu, Ag) lead to an assembly of the heterometallic clusters, the composition of which is determined by the steric bulkiness of the alkynyl groups and the flexibility of the phosphine motifs. For R = Ph, an unprecedented hexanuclear complex [Au5Cu(C2R)(4)(dpmp)(2)](2+) (1) was isolated, while for the aliphatic alkynes (R = 1-cyclohexanolyl, 2-borneolyl, 2,6-dimethyl-4-heptanolyl) a family of compounds based on a tetrametallic framework was prepared, [Au3Cu(C2R)(3)(dpmp)](+) (2, R = 1-cyclohexanolyl), [Au3M(C2R)(3)(dpep)](2) (+2) (3, M = Cu, R = 1-cyclohexanolyl; 4, M = Cu, R = 2-borneolyl; 5, M = Ag, R = 2-borneolyl), and [Au3Ag(C2R)(3)(dpep)](+) (6, R = 2,6-dimethyl-4-heptanolyl). Clusters 1, 2, and 4-6 were studied by X-ray crystallography. The NMR spectroscopic investigations showed that 1 and 3-5 are stereochemically non-rigid in solution and reversibly undergo possible dissociation (3) or isomerization (4, 5) processes. All the title complexes exhibit room temperature luminescence in the solid state in the spectral region from 414 to 566 nm, showing a dependence of emission energy on the structure and composition of the metal core. Computational studies with density functional methods were carried out to rationalize the dynamic and photophysical behavior of these compounds.
AB - The reactions of gold acetylides (AuC2R)(n) with triphosphine ligands PPh2(CH2)(n)-PPh-(CH2)(2)-PPh2 (n = 1, dpmp; 2, dpep) in the presence of M+ ions (M = Cu, Ag) lead to an assembly of the heterometallic clusters, the composition of which is determined by the steric bulkiness of the alkynyl groups and the flexibility of the phosphine motifs. For R = Ph, an unprecedented hexanuclear complex [Au5Cu(C2R)(4)(dpmp)(2)](2+) (1) was isolated, while for the aliphatic alkynes (R = 1-cyclohexanolyl, 2-borneolyl, 2,6-dimethyl-4-heptanolyl) a family of compounds based on a tetrametallic framework was prepared, [Au3Cu(C2R)(3)(dpmp)](+) (2, R = 1-cyclohexanolyl), [Au3M(C2R)(3)(dpep)](2) (+2) (3, M = Cu, R = 1-cyclohexanolyl; 4, M = Cu, R = 2-borneolyl; 5, M = Ag, R = 2-borneolyl), and [Au3Ag(C2R)(3)(dpep)](+) (6, R = 2,6-dimethyl-4-heptanolyl). Clusters 1, 2, and 4-6 were studied by X-ray crystallography. The NMR spectroscopic investigations showed that 1 and 3-5 are stereochemically non-rigid in solution and reversibly undergo possible dissociation (3) or isomerization (4, 5) processes. All the title complexes exhibit room temperature luminescence in the solid state in the spectral region from 414 to 566 nm, showing a dependence of emission energy on the structure and composition of the metal core. Computational studies with density functional methods were carried out to rationalize the dynamic and photophysical behavior of these compounds.
KW - LINEAR TETRAPHOSPHINE LIGANDS
KW - ACETYLIDE-CONTAINING CLUSTERS
KW - BRIDGING PHOSPHINE-LIGANDS
KW - DENSITY-FUNCTIONAL METHODS
KW - D(10) METAL-COMPLEXES
KW - RAY CRYSTAL-STRUCTURE
KW - STRUCTURAL-CHARACTERIZATION
KW - LUMINESCENT PROPERTIES
KW - SILVER(I) COMPLEXES
KW - BASIS-SETS
U2 - 10.1039/c3dt52658e
DO - 10.1039/c3dt52658e
M3 - Article
SN - 1477-9226
VL - 43
SP - 3383
EP - 3394
JO - Dalton Transactions
JF - Dalton Transactions
IS - 8
ER -