Luminescent rhenium(I)-dipyrrinato complexes.

The first Re(I)-dipyrrinato complexes are reported. Complexes with the general formulas fac-[ReL(CO)(3)Cl](-), fac-[ReL(CO)(3)PR(3)], and [ReL(CO)(2)(PR(3))(PR'(3))] have been prepared, where L is one of a series of meso-aryl dipyrrinato ligands. Access to these complexes proceeds via the reaction of [Re(CO)(5)Cl] with the dipyrrin (LH) to produce fac-[ReL(CO)(3)Cl](-).

Exciton coupling in coordination compounds.

This Perspective reviews the impact of exciton coupling on the spectroscopic properties of coordination compounds. Exciton coupling features arise in electronic absorption and circular dichroism spectra when chromophores are brought into close spatial proximity, for example by coordination to a metal centre. The analysis of these features can reveal much information such as the geometry of a complex and its absolute configuration.

Strongly absorbing pi-pi* states in heteroleptic dipyrrin/2,2'-bipyridine ruthenium complexes: excited-state dynamics from resonance raman spectroscopy.

A recently reported new class of ruthenium complexes containing 2,2'-bipyridine and a dipyrrin ligand in the coordination sphere exhibit both strong metal-to-ligand charge-transfer (MLCT) and pi-pi* transitions. Quantitative analysis of the resonance Raman scattering intensities and absorption spectra reveals only weak electronic interactions between these states despite direct coordination of the bipyridyl and dipyrrin ligands to the central ruthenium atom. On the basis of DFT calculations and time-dependent DFT (TD-DFT), we propose that the electronic excited states closely resemble "pure" MLCT and pi-pi* states.

Chromophoric dipyrrin complexes capable of binding to TiO2: synthesis, structure and spectroscopy.

The synthesis, characterisation, and TiO2 binding studies of a series of chromophoric complexes of 5-(4-carboxyphenyl)-4,6-dipyrrin (L(b)) are presented. The synthesis of [Ru(bipy)(L(b))2] (bipy = 2,2-bipyridine), [Rh(L(b))3], and [Pd(L(b))2] was achieved by initial coordination of 5-(4-methoxycarbonylphenyl)-4,6-dipyrrin (L(a)) followed by hydrolysis of the ester group. The carboxyl groups that are located on the peripheries of these complexes are able to engage in intermolecular hydrogen bonding interactions in the solid state, as revealed by X-ray crystallography.