Modulating the Electronic Structure of Biphenyl Metalloporphyrins

Metalloporphyrins and Porphyrins (MPs) have garnered increasing attention as potential candidates for molecular-based electronic devices and single atom catalysis. Recent studies have found that electronic structure calculations are important factors in controlling the performance of MPs as building blocks for single-molecule devices. Our study includes central 3d-metals from Sc to Cu and anchoring groups such as -SH, -SeH, and -TeH substituted at the meso-position of the porphyrin rings. We conducted Quantum chemistry calculations, primarily Density Function Theory (DFT), for geometry optimizations, calculated bond lengths, and analyzed the molecular orbitals, and electronic structure descriptors to gain insights into the reactivity trends and electronic structure of these systems. In addition to these analyses, we explored the spin multiplicity and the distribution of spin-up and spin-down electrons, which are critical factors influencing electron transport properties and the rectification behavior of metalloporphyrins in molecular junctions. The results suggest that the central metal and spin multiplicity significantly shape the electronic properties and potential reactivity of MP molecules. This study provides insights into how the selection of the central metal and control of spin channels influence the electronic structure and reactivity of metalloporphyrin molecules. This knowledge is essential for designing MP-based materials with tailored properties for diverse applications in molecular junctions, catalysis, photovoltaics, and sensing.