Four sandwich phthalocyanines with different rare earth metals (La, Y, Yb and Sc) are synthesized to investigate the influence of aggregation on nonlinear optical limiting effect. Hyperchem fitting results show that the distance between the phthalocyanine rings of the four phthalocyanine compounds is 2.81, 2.69, 2.56 and 2.38 Å for LaPc (Tetra-β-(4-nitro) lanthanum phthalocyanine), YPc (Tetra-β-(4-nitro) yttrium phthalocyanine), YbPc (Tetra-β-(4-nitro) ytterbium phthalocyanine) and ScPc (Tetra-β-(4-nitro) scandium phthalocyanine), respectively. As the radius of rare earth ions decreases, the interlayer spacing between phthalocyanine rings decreases, which greatly increases the degree of aggregation between phthalocyanine rings. As a result, the photophysical and nonlinear absorption coefficients of different rare-earth phthalocyanines also show regular changes. The nonlinear absorption coefficients of the four rare-earth phthalocyanines were LaPc (β = 1.86ⅹ10⁻¹⁰ m/W), YPc (β = 9.78ⅹ10⁻¹¹ m/W), YbPc (β = 6.63ⅹ10⁻¹¹ m/W), ScPc (β = 7.43ⅹ10⁻¹¹ m/W), respectively, indicating that the degree of aggregation between phthalocyanine rings gradually increases as the radius of rare earth metals changes from La, Y, Yb, to Sc, which inhibits the reverse saturable absorption process of the triplet states, resulting in a gradual decrease of the nonlinear absorption coefficient. The experimental results fully reveal the effect of the aggregation effect between phthalocyanine rings on photophysical and nonlinear optical properties, and would provide a theoretical basis for the design of high-performance nonlinear optical materials.

合成了四种具有不同稀土金属（La，Y，Yb和Sc）的夹心酞菁，以研究聚集对非线性光学限幅效应的影响。Hyperchem拟合结果显示，对于LaPc（Tetra-β-（4-硝基）镧系酞菁），YPc（Tetra-β-（4- （硝基）钇酞菁），YbPc（四-β-（4-硝基）y酞菁）和ScPc（四-β-（4-硝基）scan酞菁）。随着稀土离子半径的减小，酞菁环之间的层间间距减小，这大大增加了酞菁环之间的聚集度。结果是，不同稀土酞菁的光物理吸收系数和非线性吸收系数也呈现规律性变化。四种稀土酞菁的非线性吸收系数为LaPc（β=1.86ⅹ10^-10 米/ W），YPC（β=9.78ⅹ10 ^-11 米/ W），YbPc（β=6.63ⅹ10 ^-11 米/ W），SCPC（β=7.43ⅹ10 ^-11 米/ W）分别指示随着稀土金属的半径从La，Y，Yb变为Sc，酞菁环之间的聚集度逐渐增加，这抑制了三重态的反向饱和吸收过程，从而导致非线性吸收系数逐渐减小。实验结果充分揭示了酞菁环之间的聚集效应对光物理和非线性光学性质的影响，为高性能非线性光学材料的设计提供了理论依据。