Photophysics and Nonlinear Optical Properties of Tetra- and Octabrominated Silicon Naphthalocyanines

The effect of the number of bromide substituents on the photophysical and nonlinear optical properties of the tetrabrominated naphthalocyanine Br4(tBu2PhO)4NcSi[OSi(Hex)3]2 (1) and the octabrominated naphthalocyanine Br8NcSi[OSi(Hex)3]2 (2) has been investigated through various spectroscopic techniques. Absorption and emission of 1 and 2 have been studied at room temperature and 77 K to determine the spectral properties of the ground and the excited states and the lifetimes and quantum yields of formation of the excited states. There is a moderate increase of the quantum yield of the triplet excited-state formation (PhiT = 0.10 vs 0.13) and a decrease of the triplet excited-state lifetime (tauT approximately 70 vs 50 mus) from 1 to 2. These can be attributed to the stronger heavy atom effect produced by the larger number of peripheral bromide substituents in 2 considering that an excited state with a triplet manifold is involved in the excitation dynamics of both complexes 1 and 2. The quantum yields of the singlet oxygen formation (PhiDelta) upon irradiation of 1 and 2 at 355 nm were also evaluated, and a value of PhiDelta(1) = PhiDelta(2) = 0.16 was obtained. In addition to that, octabrominated complex 2 displays a larger decrease of nonlinear optical transmission for nanosecond pulses at 532 nm with respect to the tetrabrominated complex 1. The nanosecond Z-scan experiments reveal that 1 and 2 exhibit both a reverse saturable absorption and a nonlinear refraction at 532 nm. However, both the sign and the magnitude of the nonlinear refraction change from 1 to 2. For picosecond Z-scan in the visible spectral region, these two complexes exhibit only reverse saturable absorption, and the excited-state absorption cross-section increases at longer wavelengths.