Citation: ZHANG Jie, TENG Ming-Yu, DAI Guo-Liang, ZHAO Song-Lin, WANG Jia-Li, ZHANG Ping, SONG Tong-Tong. Synthesis, Characterization, Linear and Nonlinear Optical Effects of Nonsymmetrical Bipolar (D-π-A) Pyridyl Metallo Salophen Complexes[J]. Chinese Journal of Inorganic Chemistry, ;2014, 30(3): 499-505. doi: 10.11862/CJIC.2014.059 shu

Synthesis, Characterization, Linear and Nonlinear Optical Effects of Nonsymmetrical Bipolar (D-π-A) Pyridyl Metallo Salophen Complexes

  • Received Date: 29 July 2013
    Available Online: 26 September 2013

    Fund Project: 浙江省自然科学基金(No.LQ13B010001) (No.LQ13B010001)国家自然科学基金(No.21203135) (No.21203135)浙江省教育厅科研基金(No.Y201016505)资助项目。 (No.Y201016505)

  • The pyridine substituent vanillins (1a and 1b) were synthesized by still coupling reaction. New unsymmetrical metallo Salophen complexes (3a, 3b and 3c) derived from the condensation of monoamine 2 and pyridine substituent salicylaldehyde in the presence of transition metal ions (Zn2+, Ni2+) as template have been synthesized and characterized. The linear and third-order non-linear optical (two photon absorption, TPA) properties of the complexes have been measured. The emission of (3a and 3c) were in the visible range(504~516 nm) with lifetime between 4.51 to 5.18 ns and quantum yields (Φem) between 4.3% to 5.3%. Decay times with nano-second scale indicate the emissions come from the singlet states. Complexes 3a, 3b and 3c are thermally stable with onset decomposition temperatures (Td) within the range of 333 to 374 ℃. 100 fs laser pulses with the open-aperture Z-scan method was used to measure the TPA cross-sections σ(2) of 3a, 3b and 3c at 800 nm. The σ(2) could reach to 1 403 GM, which is among the largest value known for metalloSalophen complexes to date. In general, these Salophen complexes show moderate fluorescence quantum yields, larger σ(2), low cytotoxicity of zinc complexes and thermal stability. Hence, they are potentially good TPA candidates for tissue imaging work and excitation by NIR or longer-wavelength radiation is possible to increase penetration depth and reduce cell damage.
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