The design and synthesis with full structural utilization of a new type of nonlinear photonic material, Zinc(II) phthalocyanine macrocycle (Pc-pyrene), bearing binary oriented (up/down) pyrene units is reported. The novel pyrene-based macrocycle has been successfully obtained in high yield upon coupling multiple azido pyrene derivatives on a previously fabri-cated alkynyl-substituted macrocyclic platform (Pc1) via multiple tandem Cu(I)-catalysed azide-alkyne cycloaddition (CuAAC) reactions. The ultrafast nonlinear optical characteristics of both Pc1 and Pc-pyrene have been investigated in solution using a near-infrared femtosecond pulsed laser. The femtosecond Z-scan results reveal a low optical limiting threshold and a good set of figures of merit that make these macrocycles feasible for optical limiting as well as switching applications. In a major breakthrough, ultrafast laser-induced deformations in Pc-pyrene-embedded PMMA films results in a very large enhancement of the three-photon absorption coefficient at 800 nm by up to ~10⁵ times that of Pc solutions. Furthermore, the deformed Pc-pyrene PMMA films having the advantage of flexibility and possess an excellent optical limiting threshold (0.0018 J/cm²), much lower than various previously reported values, which enables them to be one of the best optical limiters.

报道了具有二元取向（上/下）pyr单元的新型非线性光子材料锌（II）酞菁大环（Pc-py）的设计和合成。通过将多个叠氮基has衍生物通过预先制备的炔基取代的大环平台（Pc1）偶联，成功地高收率地获得了新型的pyr基大环化合物。多个串联的Cu（I）催化的叠氮化物-炔烃环加成（CuAAC）反应。使用近红外飞秒脉冲激光在溶液中研究了Pc1和Pc-py的超快非线性光学特性。飞秒Z扫描结果显示出较低的光学限制阈值和良好的品质因数集，使这些大循环对于光学限制和开关应用而言是可行的。一项重大突破是，在嵌入Pc-py的PMMA薄膜中超快激光诱导的形变导致800 nm处的三光子吸收系数大大提高，最多是Pc溶液的约10 ⁵倍。此外，变形的Pc-py PMMA薄膜具有柔韧性的优点，并具有出色的光学极限阈值（0.0018 J / cm²），远低于以前报告的各种值，这使其成为最佳的光学限制器之一。