Excited states of nitro-polypyridine metal complexes and their ultrafast decay. Time-resolved IR absorption, spectroelectrochemistry, and TD-DFT calculations of fac-[Re(Cl)(CO)3(5-Nitro-1,10-phenanthroline)]

The lowest absorption band of fac-[Re(Cl)(CO)(3)(5-NO2-phen)] encompasses two close-lying MLCT transitions. The lower one is directed to LUMO, which is heavily localized on the NO2 group. The UV-vis absorption spectrum is well accounted for by TD-DFT (G03/PBEPBE1/CPCM), provided that the solvent, MeCN, is included in the calculations. Near-UV excitation of fac-[Re(Cl)(CO)(3)(5-NO2-phen)] populates a triplet metal to ligand charge-transfer excited state, (MLCT)-M-3, that was characterized by picosecond time-resolved IR spectroscopy. Large positive shifts of the v(CO) bands upon excitation (+70 cm(-1) for the A'(1) band) signify a very large charge separation between the Re(Cl)(CO)3 unit and the 5-NO2-phen ligand. Details of the excited-state character are revealed by TD-DFT calculated changes of electron density distribution. Experimental excited-state v(CO) wavenumbers agree well with those calculated by DFT. The (MLCT)-M-3 state decays with a ca. 10 ps lifetime (in MeCN) into another transient species, that was identified by TRIR and TD-DFT calculations as an intraligand (3)n pi* excited state, whereby the electron density is excited from the NO2 oxygen lone pairs to the pi* system of 5-NO2-phen. This state is short-lived, decaying to the ground state with a similar to 30 ps lifetime. The presence of an n pi* state seems to be the main factor responsible for the lack of emission and the very short lifetimes of 3 MLCT states seen in all d(6)-metal complexes of nitro-polypyridyl ligands. Localization of the excited electron density in the lowest (MLCT)-M-3 states parallels localization of the extra electron in the reduced state that is characterized by a very small negative shift of the v(CO) IR bands (-6 cm(-1) for A'(1)) but a large downward shift of the v(s)(NO2) IR band. The Re-Cl bond is unusually stable toward reduction, whereas the Cl ligand is readily substituted upon oxidation.

Synthesis, structural and emission studies of a bis (carbamoyl methyl) sulfone complex of uranyl nitrate

A new tri-functional ligand (Bu2NCOCH2SO2CH2CONBu2)-Bu-i-Bu-i (L) was prepared and characterized. The coordination chemistry of this ligand with uranyl nitrate was studied with IR, (HNMR)-H-1, ES-MS, TG and elemental analysis methods. The structure of the compound [UO2(NO3)(2)L] was determined by single crystal X-ray diffraction techniques. In the structure the uranium(VI) ion is surrounded by eight oxygen atoms in a hexagonal bi-pyramidal geometry. Four oxygen atoms from two nitrate groups and two oxygen atoms from the ligand form a planar hexagon. The ligand acts as a bidentate chelate and bonds through both the carbamoyl groups to the uranyl nitrate. An ES-MS spectrum shows that the complex retains the bonding in solution. The compound displayed vibronically coupled fluorescence emission.

Further evidence for variable synchrotron emission in XTE J1118+480 in outburst

We present simultaneous multicolor infrared and optical photometry of the black hole X-ray transient XTE J1118+480 during its short 2005 January outburst, supported by simultaneous X-ray observations. The variability is dominated by short timescales, ~10 s, although a weak superhump also appears to be present in the optical. The optical rapid variations, at least, are well correlated with those in X-rays. Infrared JHKs photometry, as in the previous outburst, exhibits especially large-amplitude variability. The spectral energy distribution (SED) of the variable infrared component can be fitted with a power law of slope α=-0.78+/-0.07, where F_ν~ν^α. There is no compelling evidence for evolution in the slope over five nights, during which time the source brightness decayed along almost the same track as seen in variations within the nights. We conclude that both short-term variability and longer timescale fading are dominated by a single component of constant spectral shape. We cannot fit the SED of the IR variability with a credible thermal component, either optically thick or thin. This IR SED is, however, approximately consistent with optically thin synchrotron emission from a jet. These observations therefore provide indirect evidence to support jet-dominated models for XTE J1118+480 and also provide a direct measurement of the slope of the optically thin emission, which is impossible, based on the average spectral energy distribution alone.