Two covalently linked porphyrin-polyoxometalate hybrids have been prepared: an Anderson-type hexamolybdate [N(C(4)H(9))(4)](3)[MnMo(6)O(18){(OCH(2))(3)CNHCO(ZnTPP)}(2)] with two pendant zinc(II)-tetraphenylporphyrins, and a Dawson-type vanadotungstate [N(C(4)H(9))(4)](5)H[P(2)V(3)W(15)O(59){(OCH(2))(3)CNHCO(ZnTPP)}] with one porphyrin. Electrochemical studies show independent redox processes for the organic and inorganic parts at usual potentials. Photophysical studies reveal an electron transfer from the excited porphyrin to the Dawson polyoxometalate, but not to the Anderson polyoxometalate. Time resolved absorption spectroscopy allows the identification of the electron transfer pathways and the determination of the time constants.

The two sp(3) hybridized fluorine atoms of a Bodipy dye have been synthetically replaced with the linear donor ligand 4-ethynylpyridine (-C≡C-Py) to form a rigid and highly symmetrical 109.5° building block in which the fluorophore subunit is vertically aligned to the plane formed by the -C≡C-Py donors. Upon reaction of the above tecton with a 90° organoplatinum acceptor unit, an intensely fluorescent rhomboid cavitand was manifested in solution. In contrast to the vast majority of coordination-driven self-assembled chromophoric systems, the present one fully conserves the excellent photophysical properties of the parent Bodipy dye. These unique features of the present metallosupramolecular entity constitute a fascinating metal-to-ligand self-assembled prototype for building compact and intensely luminescent materials with host-guest capabilities.