Influence of Pendant Arms Bearing Ligating Groups on the Structure of Bismuth Porphyrins: Implications for Labeling Immunoglobulins Used in Medical Applications
International audience; The synthesis of two picket bismuth(III) porphyrins is reported, and their crystal structures are compared. The influence of the nature of the pickets, as well as their number, is discussed in terms of stability, kinetics of metalation, structure, and distortion of the porphyrin. Unexpectedly, the resultsindicate that the coordination sphere of bismuth is not affected by different types of distortion nor is the stability of the complex. For both types of complexes, the X-ray crystallography revealed that a single arm is actually in direct interaction with the bismuth cation, thereby allowing furtherfunctionalization on the porphyrin core as the linkage with immunoglo…
Synthesis of new cylindrical macrotricyclic molecules based on tetraazamacrocycle
International audience
Functionalization of Porphyrins: Mechanistic Insights, Conformational Studies, and Structural Characterizations
The condensation of 3-chloromethylbenzoyl chloride with three atropisomers of meso-5,10,15,20-tetrakis(2-aminophenyl)porphyrin (TAPP) is reported, followed by the reaction of the anion of diethyl malonate to prepare various strapped porphyrins. According to two different geometries of the straps, the resulting preorganization of the hanging ethoxycarbonyl groups is more or less adapted to the coordination of cations such as lanthanides. The conformational study, as well as the X-ray structures of three strapped porphyrins, demonstrate that among the three atropisomers investigated in this work, only two of them lead to strapped porphyrins in which an ethoxycarbonyl group is directed towards…
Efficient photoinduced electron transfer in a porphyrin tripod-fullerene supramolecular complex via pi-pi interactions in nonpolar media.
A novel porphyrin tripod (TPZn(3)) was synthesized via "click chemistry". Three porphyrin moieties of TPZn(3) are geometrically close and linked by a flexible linker. The electron-transfer oxidation of TPZn(3) results in intramolecular pi-dimer formation between porphyrin moieties as indicated by electrochemical, vis-NIR, and ESR measurements. The cyclic voltammogram of TPZn(3) exhibited stepwise one-electron oxidation processes of three porphyrin moieties in the range from 0.58 to 0.73 V (vs SCE in CH(2)Cl(2)). When TPZn(3) was oxidized by tris(2,2'-bipyridyl)-ruthenium(III) ([Ru(bpy)(3)](3+)), the oxidized species (TPZn(3))(n+) (0n/= 3) exhibited a charge resonance band in the NIR region …