Phthalocyanine covalent frameworks doped in PMMA matrix as high performance nonlinear optical limiter

Phthalocyanine compounds are a class of macrocyclic conjugated structures with 18 π-electrons. And have better photophysical properties. However, the π-π electron interactions lead to aggregation between phthalocyanine molecules, which affects optical limiting properties. In this work, the conjugated organic small molecule antiphenylenediamine (PDA) is grafted onto the phthalocyanine conjugate system through the azo condensation reaction, and the covalent organic framework polymer (PDA-InPc) was obtained. Then it is doped into the polymethyl methylmethacrylate (PMMA) matrix to produce a phthalocyanine solid device with different thickness (PMMA-PDA-InPc). The aggregation-free phthalocyanine covalent organic frameworks avoids intramolecular aggregation of the phthalocyanine units, and dispersing it in PMMA solid devices can also reduce intermolecular π-π stacking. As a result, the fluorescence lifetime of PMMA-PDA-InPc is τ1 = 0.52 ns (A1 = 95.71%) and τ2 = 11.5 ns (A2 = 4.29%), indicating that the phthalocyanine conjugated unit exists mainly as monomers (95.71%), while the proportion as aggregates is very small (4.29%). At the input laser energy of 9 μJ, the nonlinear absorption coefficient of PMMA-PDA-InPc device is (2.2 × 10−9 m/W), which is significantly better than PMMA-InPc device (1.0 × 10−9 m/W), indicating that PMMA-PDA-InPc has improved nonlinear absorption and reverse saturation absorption. This design idea of non-aggregated phthalocyanine covalent organic frameworks and its solid device expands a new idea for the development of useable phthalocyanine optical limiters.