Photophysics of Re(I) and Ru(II) diimine complexes covalently linked to pyrene: Contributions from intra-ligand charge transfer states

The photophysical properties of Ru(II) and Re(I) polypyridyl complexes including a bis-bipyridyl pyrene ligand are presented. The complexes ([(bpy)(2)Ru](2)bpb)(4+) and [(CO)(3)ReCl(bpb)] (bpy = 2,2'-bipyridine, bpb = 1,6-bis-(4-(2,2'-bipyrid-yl)-pyrene) were designed with the intent of examining intramolecular energy migration between MLCT states localized on the metal complexes and pyrene-localized (3)(pi-pi) states. Absorption spectroscopy of both complexes containing the bpb ligand reveals that in addition to the MLCT and the pyrene-centered (1)(pi-pi) transitions, a new absorption band is observed near 400 nm for both complexes. Absorption spectral data for the Re(I) complex strongly suggest the presence of a pyrene(pi) to bpy(pi) intraligand charge transfer (ILCT) transition. Emission spectra at room temperature and at 77 K are almost identical for the Ru(II) and Re(I) complexes containing the bpb ligand. The (3)MLCT emission of related bipyridyl compounds lacking the pyrene is observed at higher energy than for the pyrene-containing complexes, ([(bpy)(2)Ru](2)bpb)(4+) and [(CO(3)ReCl(bpb)]. The Ru(II) complex emits at room temperature with a remarkably long lifetime (130 micros in degassed DMSO). This emission is also strongly sensitive to oxygen and is almost entirely quenched in an aerated solution. In addition, excited-state absorption spectra exhibit features not consistent with (3)MLCT or (3)(pi-pi) states of the parent chromophores. The combined characteristics suggest the emission arises from either (3)(pi-pi) or (3)ILCT states or a state with mixed parentage.

Investigation of the shape of the R(0) absorption line in ν3, N2O recorded from an axisymmetric supersonic free jet expansion

The hydrodynamic structure of an axisymmetric supersonic expansion can be regarded as a series of concentric divergent cones, with decreasing particle densities as the cone angle increases. Different groups of molecules therefore contribute to high-resolution absorption line shapes when optically probing the expansion in a direction perpendicular to the jet axis. These groups are distinguished by the cone angle, inducing a specific Doppler shift, and by the particle density, contributing a specific weight to the absorption intensity. As a result different broader line profiles are observed compared to room temperature spectra. This effect is investigated here selecting as the working example the R(0), ν3 absorption line in N2O recorded using a Fourier transform interferometer. Independent impact pressure and quadrupole mass spectrometric measurements are performed leading to two complementary maps of the expansion, allowing the recorded absorption line shape to be quantitatively modeled. © 2006 Elsevier Ltd. All rights reserved.

The HITRAN 2008 molecular spectroscopic database

This paper describes the status of the 2008 edition of the HITRAN molecular spectroscopic database. The new edition is the first official public release since the 2004 edition, although a number of crucial updates had been made available online since 2004. The HITRAN compilation consists of several components that serve as input for radiative-transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e. spectra in which the individual lines are not resolved; individual line parameters and absorption cross-sections for bands in the ultraviolet; refractive indices of aerosols, tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for 42 molecules including many of their isotopologues. © 2009 Elsevier Ltd.