Luminescence and Theoretical Studies of Cu(tripod)X [tripod = 1,1,1‐Tris(diphenylphosphanylmethyl)ethane; X^– = Halide, Thiophenolate, Phenylacetylide]

Abstract

. Calculations show that the emissive triplet is of mixed MLCT/LLCT character. The emission is facilitated by the rigid tetrahedral structure, which is imposed by the tripod ligand. Accordingly, a distortion towards a square-planar geometry, which should occur upon MLCT excitation, is pre-

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

“…Various copper(I) phosphane complexes are luminescent in the solid state at room temperature, and in many cases the luminescence is found to be a phosphorescence. [10] Although the nature of the emissive excited states of these compounds has not been yet definitively clarified recent TD-DFT calculations on some related complexes [8] showed the luminescence to have mixed character between metalligand charge transfer (MLCT) of the type Cu I Ǟ π*(PPh 2 ) Figure 2. Absorption spectra of complexes 1 (solid line) and 2 (dashed line) simulated at the SAOP/TZP level in the gas phase (band width of 15 nm).…”

“…Accordingly, in the present study we exploited the structural, spectroscopic (luminescent), bonding and electronic properties of some mixed-ligand copper(I) complexes formulated as [Cu(κ 3 -triphos)(thiolate)], using both experimental and computational (DFT and TD-DFT) methodologies in conjunction with singlecrystal X-ray studies for two of them. Furthermore inspired by a recent theoretical study on the luminescence of four [Cu(κ 3 -triphos)X] derivatives, [8] we instigated to further explore the relationship between structure and luminescence and evaluate the impact of the thiolate ligand on the luminescence properties of the new copper(I) complexes.…”

Alkynyl triphosphine copper complexes: synthesis and photophysical studies

“…37 Due to a pronounced tendency of the alkynyl ligands to bind two or more Cu(I) centers through σ−π coordination mode a significant number of tri-and tetranuclear species has been described 37, 38 but surprisingly no monomeric alkynyl complexes were characterized up to date. In this context it is worth mentioning a congener alkynyl-phosphine compound bearing an aliphatic tripod ligand, that initially thought to be monomeric, 30 which was later described as a dimer {Cu(μ2-C≡CPh)(triphos)}2 (triphos = (PPh2CH2)3CMe), 35 with only two P atoms involved in binding to the metal ion. Solution behavior of the complexes 1-10 was investigated by the 1 H and 31 P{ 1 H} NMR spectroscopy.…”

Copper(I) binap complexes (binap=(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl). Luminescence from IL and LLCT states

“…p * (phenyl) states have been suggested to be the origin of emissions. Moreover, metal-centered ds excited states of Cu(I) [3] as well as LLCT states of mixed-ligand complexes with phenylphosphines as CT acceptor [4] are also important. All these states occur at relatively high but comparable energies.…”

“…binap LLCT and I À ? phenylphosphine LLCT bands of [Cu I (binap)(hfac)] [20] and Cu I (tripod)I [4] with hfac = hexafluoroacetylacetonate and tripod = tris(diphenylphosphinomethyl)ethane, respectively. The LLCT state of [Cu(binap)I] 2 is emissive.…”