Electronic, geometrical and photophysical facets of five coordinated porphyrin N-heterocyclic carbene transition metals complexes: A theoretical study

In the realm of dye sensitized solar cells (DSSCs), the 3d transition metals as photosensitizers are scarcely studied. In the present work, electronic structures, FMO, MEP surfaces, NBO analysis, energetics and photophysical properties of earth abundant metals (Mn, Fe and Co) based metalloporphyrins coordinated with NHC-carbene have been explored by using DFT and TDDFT calculations. According to formation energies and energy decomposition analysis (EDA), the cobalt based metalloporphyrins species are found to be more stable while in contrast manganese based species are predicted as more reactive among all. Also, from the ligation point of view, the TPP (meso-tetraphenylporphyrin) ligand forms more steady and rigid coordination as compare to the TTP (meso-tetratolylporphyrin) ligand. FMO analysis also support these observations. NBO and SNO results support the electronic configurations as well as unveil the controversial bonding pattern of NHCcarbon and metal atom and found that there is σ-bonding present between the metal and the NHCcarbon by the overlapping of sp-hybridized orbitals of carbenecarbon and sp/d hybrid orbital of the metal atom. TDDFT results show that the highest light harvesting efficiency (LHE) of all the studied species is found under the range of 360 nm − 380 nm (λ) and this may due to the presence of longer π-conjugations. In-depth investigation of this work may help to design new robust energy harvesting systems for high energy conversion efficiency based on earth abundance metals. Our results are in well agreement with the available experimental findings.