2-(Pyridin-2-yl)-1,3-oxathiane

The title compound, C9H11NOS, exhibits a unique structural motif, with free rotation of the aliphatic oxathiane ring about the C—C bond connecting this moiety to the aromatic pyridine ring. The structure elucidation was undertaken due to its potential as a bidentate ligand for organometallic complexes. The oxathiane ring adopts the expected chair conformation, with the S atom in proximity to the N atom on the pyridine ring. The corresponding S—C—C—N torsion angle is 69.07 (14)°. In the crystal, mol­ecules aggregate as centrosymmetric pairs connected by pairs of C—H⋯N hydrogen bonds

Intrapreneurship in the Spanish context : a regional analysis

The objective of this article is to examine the influence of internal and external (environmental) factors on intrapreneurship in the Spanish context, considering differences among regions. Methodologically, the study applies logistic regression and uses data from the Spanish Global Entrepreneurship Monitor for the year 2011. The main findings of the research show through a double conceptual framework (resource-based theory and institutional economics) the direct effect of both internal factors – opportunity recognition and social capital – and environmental factors – fear of failure and education – on intrapreneurship. In addition, the role of fear of failure is reinforced as it has the indirect (moderating) effect; this effect is particularly relevant in lower income regions. The study contributes both theoretically (developing literature and provoking discussion in the field of intrapreneurship) and empirically (providing useful insights for the design of governmental policies for fostering entrepreneurial activities within firms)

Excited state properties of Rh(phi)_2(phen)^(3+) and related complexes: a strong photooxidant

The excited state properties and reactivity of Rh(phi)_2(phen)^(3+) (phi = 9,10-phenanthrenequinone diimine, phen = 1,10-phenanthroline) were investigated and compared to those of related rhodium(III) and zinc(II) complexes. At 77 K Rh(phi)_2(phen)^(3+) exhibits LC^3ππ∗ dual emission from both phi and phen ligands, whose energies are 2.8 eV and 3.0 eV, respectively, with a biexponential decay that can be fit to 5 ns (98%) and 60 ns (2%) lifetime components. A longer-lived transient is observed by transient absorption both at 77 K and 298 K, which decays monoexponentially with a time constant of 900 ns and 235 ns at each temperature, respectively, in ethanol. The transient can be attained with visible excitation (420 nm to 532 nm) and it is assigned to be intra-ligand charge transfer (ILCT) in nature. It was determined from transient absorption experiments that the ILCT excited state of Rh(phi)_2(phen)^(3+) lies approximately 2.0 eV above the ground state and that it is a powerful oxidizing agent with E_(12)([Rh]^(3+∗/2+))≈2.0V versus NHE. The transient absorption experiments with electron donors reveal that the one-electron reduced Rh(phi)_2(phen)^(2+) absorbs at 540 nm with ε ≈ 3300 M^(−1)cm^(−1)

Reply to the Comment on “Resonance Raman Investigation of Ru(phen)_2dppz^(2+) and Related Complexes in Water and in the Presence of DNA”

Our recent paper describes the rR spectra of Ru(phen)_2dppz^(2+), Ru(phen)_2(F_2-dppz)^(2+), and Os(phen)_2(dppz)^(2+) (phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2‘,3‘-d]phenazine, F_2-dppz = 7,8-difluoro-dppz) obtained utilizing 354.7 nm excitation (fwhm ∼ 10 ns). The spectra collected for Ru(phen)_2(F_2-dppz)^(2+) and Os(phen)_2(dppz)^(2+) were assigned to the ground state of the complexes at both high and low pulse energies. In the case of Ru(phen)_2dppz^(2+), the power dependence of the peaks at 1365 and 1453 cm^(-1) were consistent with an excited state. Our interpretation described below and on the recent paper was not based on the assumption that the ^3ππ* state of the dppz ligand lies below the MLCT in Ru(phen)_2dppz^(2+), but rather that pumping directly into the dppz ^1ππ* manifold could lead to trapping of the excitation at short time scales on the lowest LC dppz state (^3ππ*) if crossing to the MLCT required activation. Lowering of the MLCT relative to the ^3ππ* in Ru(phen)_2(F_2-dppz)^(2+) and Os(phen)_2(dppz)^(2+) would result in lowering the activation barrier and much faster crossing to the MLCT

Excited state properties of Rh(phi)_2(phen)^(3+) and related complexes: a strong photooxidant

The excited state properties and reactivity of Rh(phi)_2(phen)^(3+) (phi = 9,10-phenanthrenequinone diimine, phen = 1,10-phenanthroline) were investigated and compared to those of related rhodium(III) and zinc(II) complexes. At 77 K Rh(phi)_2(phen)^(3+) exhibits LC^3ππ∗ dual emission from both phi and phen ligands, whose energies are 2.8 eV and 3.0 eV, respectively, with a biexponential decay that can be fit to 5 ns (98%) and 60 ns (2%) lifetime components. A longer-lived transient is observed by transient absorption both at 77 K and 298 K, which decays monoexponentially with a time constant of 900 ns and 235 ns at each temperature, respectively, in ethanol. The transient can be attained with visible excitation (420 nm to 532 nm) and it is assigned to be intra-ligand charge transfer (ILCT) in nature. It was determined from transient absorption experiments that the ILCT excited state of Rh(phi)_2(phen)^(3+) lies approximately 2.0 eV above the ground state and that it is a powerful oxidizing agent with E_(12)([Rh]^(3+∗/2+))≈2.0V versus NHE. The transient absorption experiments with electron donors reveal that the one-electron reduced Rh(phi)_2(phen)^(2+) absorbs at 540 nm with ε ≈ 3300 M^(−1)cm^(−1)

Ligand-Specific Charge Localization in the MLCT Excited State of Ru(bpy)_2(dpphen)^(2+) Monitored by Time-Resolved Resonance Raman Spectroscopy

Time-resolved resonance Raman spectroscopy has been employed to examine the location of the promoted electron in the metal-to-ligand charge-transfer (MLCT) excited state of Ru(bpy)_2(dpphen)^(2+) (bpy) = 2,2'-bipyridine; dpphen = 4,7-diphenyl-1,10-phenanthroline). Variations in the environment about Ru(bpy)_2(dpphen)^(2+) shift the localization of charge in the MLCT excited state from bpy in neutral micelles (Brij 35) to dpphen in the presence of DNA and anionic surfactants (C_(12)H_(25)OSO_3Na, C_(10)H_(23)OSO_3Na, and C_8H_(21)OSO_3Na), whereas in water the electron is localized on both ligands. The shifts in the electronic absorption spectrum and the dependence of the ground-state resonance Raman (rR) signal with excitation wavelengths coincident with the high- and low-energy sides of the MLCT absorption band are consistent with a lowering of the energy of the Ru(II)-dpphen transition with respect to that of bpy in anionic micelles