Effect of bromination on the optical limiting properties at 532 nm of BODIPY dyes with p-benzyloxystyryl groups at the 3,5-positions

The optical limiting (OL) properties of 3,5-di-p-benzyloxystyrylBODIPY dyes that contain both protons and bromine atoms at the 2,6-positions have been investigated by using the Z-scan technique at 532 nm on the nanosecond timescale. There is relatively weak absorbance at 532 nm under ambient light conditions, because the incorporation of p-benzyloxystyryl groups at the 3,5-positions results in a ca. 140 nm red shift of the main BODIPY spectral band to the 640-670 nm range. Reverse saturable absorbance (RSA) profiles that are consistent with an excited state absorption (ESA) mechanism involving the T1 and/or S1 states are observed in CH2Cl2 solution. Second order hyperpolarizability values of ca. 8 × 10−30 esu are obtained and this demonstrates that the dyes are potentially suitable for use in OL applications at 532 nm. There is a slight enhancement of the OL properties upon bromination, due to increased intersystem crossing to the triplet manifold, but the enhancement of the OL properties is less significant than has been observed with metal phthalocyanine complexes.