(2,2′-Bipyridyl)dicarbonylbis(triethoxyphosphine-κ P )rhenium(I) hexafluorophosphate

In the title compound, [Re(C10H8N2)(C6H15O3P)2(CO)2]PF6, the carbonyl ligands are mutually cis and lie trans to the N donors of the 2,2'-bipyridyl ligand, while the triethoxy­phosphine ligands are mutually trans. The ReI centres exhibit approximate octa­hedral coordination, the major distortions from which arise from the narrow bite angle of the 2,2'-bipyridyl ligand which is expressed in the N-Re-N angles of 74.0 (3) and 74.3 (3)°. There are two cations and two anions in the asymmetric unit. The title compound is of inter­est because it has been shown to be a photocatalyst for CO2 reduction [Ishitani, George, Ibusuki, Johnson, Koike, Nozaki, Pac, Turner & Westwell (1994). Inorg. Chem. 33, 4712-4717]

UV-vis and IR monitored picosecond transient spectroscopic study of photoinduced electron transfer involving DNA-intercalated Ruthenium complexes - a role for proton transfer ?

info:eu-repo/semantics/nonPublishe

Dynamics of benzene molecules situated in metal-organic frameworks

In this paper, we investigate the gyroscopic motion of a benzene molecule C6H6, which comprises an inner carbon ring and an outer hydrogen ring, and is suspended rigidly inside a metal-organic framework. The metal-organic framework provides a sterically unhindered environment and an electronic barrier for the benzene molecule. We model such gyroscopic motion from the inter-molecular interactions between the benzene ring and the metal-organic framework by both the Columbic force and the van der Waals force. We also capture additional molecular interactions, for example due to sterical compensations arising from the carboxylate ligands between the benzene molecule and the framework, by incorporating an extra empirical energy into the total molecular energy. To obtain a continuous approximation to the total energy of such a complicated atomic system, we assume that the atoms of the metal-organic framework can be smeared over the surface of a cylinder, while those for the benzene molecule are smeared over the contour line of the molecule. We then approximate the pairwise molecular energy between the molecules by performing line and surface integrals. We firstly investigate the freely suspended benzene molecule inside the framework and find that our theoretical results admit a two-fold flipping, with the possible maximum rotational frequency reaching the terahertz regime, and gigahertz frequencies at room temperature. We also show that the electrostatic interaction and the thermal energy dominate the gyroscopic motion of the benzene molecule, and we deduce that the extra energy term could possibly reduce the rotational frequency of the rigidly suspended benzene molecule from gigahertz to megahertz frequencies at room temperature, and even lower frequencies might be obtained when the strength of these interactions increases.Yue Chan, James M. Hil