Complexes of Transition Metals with Petroleum Porphyrin Ligands: Preparation and Evaluation of Catalytic Ability

In the present work, the first data on the catalytic activity of d-metal complexes of petroleum porphyrins obtained via two-stage re-metallization (acid demetallization with subsequent metalation) of high-purity petroleum vanadyl porphyrins are presented. During acid demetallization of petroleum vanadyl porphyrins, the highest yield (49%) and spectral purity of free petroporphyrin bases were achieved with concentrated sulfuric acid and a diluted solution of vanadyl porphyrins in chloroform. In the series of divalent cations of Mn, Fe, Co, Ni, Cu, and Zn, only the last four metals are complexed with demetallated petroporphyrins without significant changes in their component composition, whereas the interaction with Mn and Fe cations causes an evident structural transformation or even full degradation of petroporphyrin macrocycles, respectively. The composition and spectral purity of petroleum porphyrin-containing reactants and products were analyzed by FT-IR, UV-Vis, NMR, and MALDI-TOF mass spectroscopic methods. The obtained petroporphyrin-based d-metal complexes were assayed by the reaction of 2-mercaptoethanol oxidative dimerization, in which the copper porphyrins exhibited the highest catalytic activity.

Investigation of 1064-nm Pumped Type II SPDC in Potassium Niobate for Generation of High Spectral Purity Photon Pairs

The generation and detection of nonclassical light of about 2 μm has good potential in an emerging field of high-sensitivity metrology, especially gravitational wave detection, as well as free-space quantum communication. A pair of photons is generated through a spontaneous parametric down-conversion (SPDC) process in a nonlinear optic crystal, which can be properly entangled in a spatial region where two beams with each polarization overlap or in a Sagnac-loop interferometer configuration. We investigated theoretically and numerically Type II SPDC in a potassium niobate (KNbO3, KN) crystal, which is useful as a material platform for generating photon pairs of high spectral purity in the 2-μm range. The technique is based on the frequency degenerate SPDC under Type II extended phase matching (EPM). We described the EPM characteristics of KN and showed that it is practically feasible for a 1064-nm pumped SPDC under moderate temperature conditions. The effective nonlinear optic coefficient of KN is at least four-times larger than those of other crystals using the Type II EPM approach, which implies a significant improvement in SPDC efficiency. The joint spectral analysis showed that a pair of photons can be generated with a high purity of 0.995 through proper pump filtering.