Synthesis Of Naphthalene Phthalocyanine Complexes Containing Nitrogen And Their Third - Order Nonlinear Optical Properties

The preparation of nonlinear optical materials is very important for the development of photonics technique. Phthalocyanine derivatives have outstanding nonlinear optical properties due to there are particular structures, and have become an active part in the field of optical nonlinearity .In this paper, tertraacetamide metallonaphthalocyanines[MNc(NHCOCH3)4 M=Co, Ni, Cu, Zn] , tertrapyridyloxy metallophthalocyanines [MPc(OC5H4N)4 M=Fe, Co, Ni, Cu, Zn, Pb, In] and tertraquaternaryammoniumsalt metallophthalocyanines [MPc(NMe3I)4 M=Co, Ni, Cu, Zn] were designed and synthesized for fabricating solid material with larger optical nonlinearity. The compounds were characterized by MALDI-TOF-MS, IR, UV-vis, 1HNMR, etc. Electrostatic self-assembled films containing MPc(NMe3I)4/PSS (Ni、Cu、Zn) were fabricated by electrostatic self-assembled technique. The procedure for fabricating the films was monitored, and thickness and linear susceptibility of the films were obtained.The third-order nonlinear optical (NLO) properties of MNc(NHCOCH3)4、MPc(OC5H4N)4 and MPc(NMe3I)4 were investigated using Z-scan technique with laser pulses of 130 femtosecond at the wavelength of 800 nm. The third-order NLO properties of MPc(NMe3I)4 were investigated using Z-scan technique with laser pulses of 4 nanosecond at the wavelength of 532 nm. Effect of center metals, peripheral substitutes and laser pulse width on third-order nonlinearities were investigated.The results showed that the second-order molecular hypersusceptibility of complexes could be enhanced with femtosecond pulses when transition metal is inserted into the central position of the macrocycle system and the 3d orbit of the central atom is open-shell. Theγvalue of MPc(OC5H4N)4 is very large probably because the axial substituent is attached to the central atom. The dissolubility of complexes in organic solvent is one of influencing factors, and theγvalue was enhanced with the improvement of solubility. The induced effect of electron-acceptor group (-NMe3I) on the conjugated system is stronger than electron-donator group-OC5H4N and-NH2. Therefore, theγvalue is very large when center metal and conjugated system are separate same, and the electron-acceptor group is inserted into complexes, showing the following increasing order:γ[CoPc(OC5H4N)4] <γ[CoPc(NMe3I)4] andγ[ZnPc(NH2)4] <γ[ZnPc(NMe3I)4]. When the laser intensity is the same and pulse width are not the same, the mechanism for the nonlinear absorption of complexes is different. When the samples are excitated by femtosecond pulses with the on-axis peak intensity of 2.0×1012 W/m2, the samples show saturable absorption effect. But, when the samples are excitated by nanosecond pulses with the same light intensity, the samples show reverse saturable absorption effect.