Bis(6-diphenylphosphino-acenaphth-5-yl)sulfoxide. A New Ligand for Late Transition Metal Complexes

The synthesis of the new ligand bis(6-diphenylphosphinoacenaphth-5-yl)sulfoxide, [6-(Ph2P)-5-Ace-6](2)-SO (1), is presented along with six transition metal complexes thereof, namely,1 center dot MCl (M = Rh, Cu, Ag, Au) and1 center dot MCl2(M = Ni, Pd). Within these novel complexes, close metal-sulfur distances are observed and the nature of the M-S coordination, as well as the response of the(+)S-O(-)bond, are investigated in detail with a set of spectroscopic, crystallographic and real-space bonding indicators

Peri-substituted phosphorus-tellurium systems – an experimental and theoretical investigation of the P∙∙∙Te through-space interaction

The authors are thankful to the EPSRC, the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea, the School of Chemistry St. Andrews, and EaStCHEM for support.A series of peri-substituted phosphorus-tellurium systems R’Te–Acenap–PR2 (R’ = Ph, p-An, Nap, Mes, Tip; R = iPr, Ph) exhibiting large “through space” spin-spin coupling constants and the “onset” of three-centre four-electron type interactions are presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metal-coordination (Pt, Au) is discussed using NMR spectroscopy, single crystal X-ray diffraction, and advanced DFT studies including NBO, AIM and ELI-D analyses.PostprintPeer reviewe

Dibenzyl Isophthalates as Versatile Hosts in Room Temperature Phosphorescence Host-Guest Systems

We report a series of dibenzyl isophthalates (DBIs) as versatile hosts for room-temperature phosphorescence (RTP) systems, leading to host-guest systems with quantum yields (QY) of up to 77 % or lifetimes of up to 21.0 s for the guest coronene d12. Furthermore, a 4,4’-Br substituted DBI was used to form host-guest RTP systems with 15 different aromatic guest molecules, to tune the phosphorescence emission color from blue to red and to demonstrate the versatility of the host. Mechanistic insights were gained through a host-guest-matrix system which shows RTP already by trace combinations of a 4,4’ Br DBI host (0.10 wt%) and a pyrene-d10 guest (0.01 wt%) in an otherwise non-RTP-emissive aromatic matri

Lattice response to the radiation damage of molecular crystals: radiation-induced versus thermal expansivity.

The interaction of intense synchrotron radiation with molecular crystals frequently modifies the crystal structure by breaking bonds, producing fragments and, hence, inducing disorder. Here, a second-rank tensor of radiation-induced lattice strain is proposed to characterize the structural susceptibility to radiation. Quantitative estimates are derived using a linear response approximation from experimental data collected on three materials Hg(NO3)2(PPh3)2, Hg(CN)2(PPh3)2 and BiPh3 [PPh3 = triphenylphosphine, P(C6H5)3; Ph = phenyl, C6H5], and are compared with the corresponding thermal expansivities. The associated eigenvalues and eigenvectors show that the two tensors are not the same and therefore probe truly different structural responses. The tensor of radiative expansion serves as a measure of the susceptibility of crystal structures to radiation damage

Bis(6-Diphenylphosphinoacenaphth-5-yl)Telluride as a Ligand toward Manganese and Rhenium Carbonyls

The reaction of the previously known bis(6-diphenylphosphinoacenaphthyl-5-)telluride (6-Ph2P-Ace-5-)2Te (IV) with (CO)5ReCl and (CO)5MnBr proceeded with the liberation of CO and provided fac-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (fac-1: M = Re, X = Cl; fac-2: M = Mn, X = Br), in which IV acts as bidentate ligand. In solution, fac-1 and fac-2 are engaged in a reversible equilibrium with mer-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (mer-1: M = Re, X = Cl; mer-2: M = Mn, X = Br). Unlike fac-1, fac-2 is prone to release another equivalent of CO to give (6-Ph2P-Ace-5-)2TeMn(Br)(CO)2 (3), in which IV serves as tridentate ligand