Platinum(ii) and palladium(ii) complexes with electron-deficient meso-diethoxyphosphorylporphyrins: synthesis, structure and tuning of photophysical properties by varying peripheral substituents.

A series of electron-deficient platinum(ii) and palladium(ii) meso-(diethoxyphosphoryl)porphyrins, namely [10-(diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato]palladium(ii) (PdDTolPP), {10-(diethoxyphosphoryl)-5,15-bis[p-(methoxycarbonyl)phenyl]porphyrinato}palladium(ii) [PdD(CMP)PP], [10-(diethoxyphosphoryl)-5,15-dimesitylporphyrinato]palladium(ii) (PdDMesPP), [5-(diethoxyphosphoryl)-10,15,20-trimesitylporphyrinato]palladium(ii) (PdTMesPP) and the corresponding platinum(ii) compounds, were synthesized and structurally characterized in solution by means of H, C, P NMR spectroscopies and in the solid state by single crystal X-ray diffraction [PdDTolPP, PdD(CMP)PP and PtD(CMP)PP]. Their optical and photophysical properties (UV-vis absorption, luminescence and excitation spectra, phosphorescence quantum yields and lifetimes) were also determined. The complexes under investigation emit at room temperature in the near-infrared region (670-770 nm).

Hybrid organic-inorganic supramolecular systems based on a pyridine end-decorated molybdenum(ii) halide cluster and zinc(ii) porphyrinate.

Herein, first examples of supramolecular hybrid organic-inorganic cluster-porphyrin [CP (n = 2, 6)] systems constructed via metal-ligand coordination have been reported. The pyridine end-decorated Mo(ii) halide cluster ((BuN)[{MoI}(OOC-CHN)]), possessing remarkable photophysical properties, was chosen as the inorganic part and A-type zinc porphyrin 5,15-bis[(p-tolyl)porphyrinato(2-)]zinc was selected as the organic part. The crystal structures of CP and CP hybrids have been characterised by single crystal X-ray diffraction.