Two coordinatively linked supramolecular assemblies constructed from highly electron deficient porphyrins

The synthesis of a pair of electron-deficient porphyrin building blocks and their resulting coordinatively linked supramolecular assemblies are described. The perfluorophenyl substituted porphyrins feature pendant pyridines which, upon reaction with Re(CO)₅Cl assemble into discrete dimers and tetramers, as dictated by the geometry of the porphyrin monomer. The resulting supramolecular complexes as well as their constituent porphyrins display several interesting and potentially useful properties owing to the electron-withdrawing nature of the perfluorophenyl funtionalities. Structural, spectroscopic, and electrochemical data indicate that the electron-deficient porphyrins remain planar, allowing for modulation of spectral and redox properties, as well as for enhancement of the affinity of the porphyrins for Lewis-basic ligands.