Long-Range Intramolecular Spin Coupling through a Redox-Active Bridge upon Stepwise Oxidations: Control and Effect of Metal Ions

Dinickel(II) and dicopper(II) porphyrin dimers have been constructed in which two metalloporphyrin units are widely separated by a long unconjugated dipyrrole bridge. Two macrocycles are aligned somewhat orthogonally to each other, whileoxidation of the bridge generates a fully pi-conjugated butterfly-like structure, which, in turn, upon stepwise oxidations by strongeroxidants result in the formation of the corresponding one- and two-electron-oxidized species exhibiting unusual long-range charge/radical delocalization to produce intense absorptions in the near-infrared (NIR) region and electron paramagnetic resonance (EPR)signals of a triplet state due to interaction between the unpaired spins on the Cu(II) ions. Although the two metal centers have alarge physical separation through the bridge (more than 16 A), they share electrons efficiently between them, behaving as a singleunit rather than two independent centers. Detailed UV-vis-NIR, electrospray ionization mass spectrometry, IR, variable-temperature magnetic study, and EPR spectroscopic investigations along with X-ray structure determination of unconjugated, conjugated, and one electron-oxidized complexes have been exploited to demonstrate the long-range electronic communication through the bridge. The experimental observations are also supported by density functional theory (DFT) and time-dependent DFT calculations. The present study highlights the crucial roles played by a redox-active bridge and metal in controlling the long-range electronic communication.