Optical properties of meso-tetra(sulphonatophenyl) porphyrins (TPPS ₄) and their Fe ³⁺, Mn ³⁺, Zn ²⁺ complexes with different pH values studied using by picosecond pulse trains

Abstract

Applying picosecond pulse trains propagating in meso-tetra(sulphonatophenyl) porphyrins and their Fe 3+, Mn 3+, Zn 2+ complexes, we studied the nonlinear dynamics at different pH values. The pulse train at wavelength 532nm is comprised of 20 subpulses with 70ps width and 13ns spacing. We simplified the energy structures of porphyrins and metalloporphyrins to five-level models. In solving coupled rate equations and two-dimensional paraxial field, we used Crank-Nicholson numerical method to do the calculations. The results revealed that in irregular metalloporphyrins with central paramagnetic ion Mn 3+ or Fe 3+, the central ion would act as electron acceptor, which leads to charge transfer of unpaired metal electron to the porphyrin ring π conjugated system, and strengthen the spin–orbit coupling of electronic systems and weaken the transition prohibition between electronic states in porphyrins. However regular metalloporphyrins with central diamagnetic ion Zn 2+ has similar optical properties to free base porphyrins, and Zn 2+ TPPS 4 has much longer excited state lifetimes and slower intersystem crossing. In solutions, hydrogen bond would be formed to porphyrin, which can change the transitions of π electrons and thus the charge transfer can be strengthened in the porphyrin ring. In weak intensity region with linear absorption, nonprotonated porphyrins with high pH value show better optical limiting (OL) effect. Conversely in high intensity region, protonated porphyrins with low pH value show better OL effect. Besides, increasing interaction distances of porphyrins and metalloporphyrins with laser pulses is another important factor to raise the OL effects.