(133g) Novel Organometallic-Nanocarbon Complexes for Electrochemical Applications

In this work, we report a theoretical study on novel organometallic-nanocarbon complexes for electrochemical and catalytic applications.  These materials include the N-heterocyclic-transition metal(NhTM)-nanocarbon complexes (pyrrole, pyrazole, and triazole) and porphyrin-transition metal-nanocarbon complexes (PORTM), with TM = Fe, Zn, and Mn. The geometries, binding energies, electronic structures, and magnetic properties of these materials are investigated using density functional theory (DFT) methods.

These complexes are similar to our previous work on cyclopentadienyl-transition metal (CpTM) functionalized nanocarbons, which included both pristine and B-doped carbon substrates. In comparison, the binding energies of the NhTM-nanocarbon complexes with the carbon substrates are predicted to be even greater than those of CpTM (which surpassed the intramolecular binding energy within ferrocene, a molecule with a similar structure and chemical characteristics). The electronic structures and magnetic properties of the NhTM-nanocarbon complexes are also predicted from band structure analyses, natural bond order partial charges, and deformation charge density analyses.   These complexes exhibit metallic band structures with strong magnetic momenta, indicating good conductivity for electrochemical applications and potential magnetic applications. In addition, the redox potentials and the charge transfer mechanisms in different solvents are calculated using DFT, combined with the conductor-like polarizable continuum model (CPCM) solvation technique.