Electronic Structural Characterization of Porphyrnoids and Charge Transfer Complexes

Ligand field and charge transfer transitions are critical to a variety of photochemical and electrochemical transformations. Using fundamental insight from a number of advanced spectroscopic and theoretical techniques (i.e. EAS/spectroelectrochemistry, EXAFS/XANES, MCD, TDDFT/CASSCF), we aim to identify key electronic transitions and structural properties that contribute to various modes of reactivity. We are presently interested in Lewis acid effects on mono-/multimetallic cyanide complexes and metalloporphyrinoids for applications in photo-/electrocatalysis and redox flow batteries. 

(Left Diagram) Orbital splitting with intermediate spin-orbit coupling and simultaneous deconvolution of (a) UV-vis-NIR and (b) MCD spectra for Lewis acid derivatized hexacyanoosmate and transition assignments.

(Above) Effects of Lewis basic alkylimidazolium ionic liquids on the Soret band transitions in manganese tris(pentafluorophenyl)corrole (Mn(tpfc)).