Ethylenediamine-modified graphene oxide covalently functionalized with a tetracarboxylic Zn(II) phthalocyanine hybrid for enhanced nonlinear optical properties

Tetracarboxylic Zn(II) phthalocyanine-amino functionalized graphene oxide (ZnPcC4-NGO) hybrid materials have been prepared by a covalent functionalization method. The characterizations indicate that the amino-functionalization of GO has an important influence on the structure and photophysical properties of the ZnPcC4-NGO hybrid. The ZnPcC4-NGO hybrid exhibits enhanced photo-induced electron transfer or energy transfer (PET/ET), compared to the ZnPcC4 covalent functionalized GO (ZnPcC4-GO), owing to the presence of the extended sp(2) carbon configurations, along with the partial reduction of the NGO nanosheets and the introduction of electron-donating ethylenediamine. The nonlinear optical (NLO) properties of the hybrids were investigated using the Z-scan technique at 532 nm with 4 ns laser pulses. The results show that the efficient covalent functionalization and partial reduction of NGO cause the ZnPcC4-NGO hybrid to possess evidently larger NLO properties than the individual NGO, ZnPcC4 and the ZnPcC4-GO hybrid. The enhanced NLO performance can be attributed to the increased excited state absorption from the extended sp(2) carbon configurations of the NGO moiety, reverse saturable absorption arising from ZnPcC4 moiety, and the contribution of the efficient PET/ET process between the ZnPcC4 and NGO moieties in the hybrid.