Core modified freebase porphyrins in glass matrix for nonlinear optical properties

Two different types of freebase porphyrins with variation in the central core, namely H2TPP (meso-5,10,15,20- tetrakis phenyl porphyrin) and HSTPP (meso-tetrakis 5,10,15,20-tetra-phenyl-23-H-21-thiaporphyrin) were introduced into the borate glass matrix and developed the thin films by melt quenching technique. Due to core modification and extended non-planarity in the glass matrix, the absorption spectrum of HSTPP shows a strong redshift in the soret and Q bands. Emission spectra of HSTPP show an intense emission at 739 nm (S1 → S0) and ~ 505 nm due to coordination of boron atom at the central core and freezing of N-BO3 vibrations furnishes slow relaxation from higher energy states. Comparison studies are made by treating with BF3O(C2H5)2 to mimic structure in the borate glass matrix due to boron coordination at the central core. The excited state lifetimes are shortened due to BF3 interaction in the solution as well as in the borate glass matrix endowing its potential to develop the optical limiting devices. Nonlinear optical studies reveal reverse saturable absorption (RSA) behaviour in the picosecond (ps) region and show enhanced two photon absorption (TPA) by core modification. Optical power limiting measurements on HSTPP in glass matrix delivers a better limiting threshold value of 15.2 mJ/cm2.