无机-有机杂化近红外三阶非线性光学功能材料合成与性能研究

Research target of the proposed studies is to design and prepare the inorganic-organic hybrid materials for near-infrared third-order nonlinear optical functions with a variety of technologically important applications. Three kinds of binary important NLO-active materials can be created as follows: 1) Various pi-conjugated organic-bridging units and chuster-building blocks of different electron structures will be designed and applied to construct the functional heterothiometallic cluster-based organic frameworks; 2) Syntheses of dipolar and multipolar pi-conjugated complexes and derivatives with electronically-innocent but solubilizing metal phenyl alkynyl units, conjugated with organic, organometallic, and coordination complex moieties, in a range of centrosymmetric metal-terminated (Ru, Fe, Os, Ir) configurations such as superchains, cruciforms, stars and dendrimers; 3) A variety of large pi-conjugated structures, axially or radially conjugated modified porphyrins and phthalocyanines as well as their derivatives, various terminal connection models and synthetic processes will be applied to build porphyrin- or phthalocyanine-conjugated functionzalized graphene or multi-/single-wall carbon nanotubes. We will try to investigate and optimize these binary conjugated structures with the ultrafast third-order nonlinear optical properties in the near infrared region. This will afford these systematically-modified inorganic-organic binary conjugated structures suitable for developing the correlations between their structures and near-infrared nonlinear optical properties at the molecular level. We will aslo attempt to elucidate the physical mechanism and dynamics process of the near-infrared optical nonlinearity in these binary pi-conjugated structures, with the important goal to the construction of the practically applicable third-order nonlinear optical materials and devices at the key near-infrared wavelengths.

本项目的研究目标是设计与制备无机-有机杂化近红外三阶非线性光学功能材料。我们将通过设计并应用: 1) 多种pi共轭有机桥连基团和电子结构特征的金属簇合物构建单元创制过渡金属簇合物-有机框架结构, 2) 多种电子良性的、可溶性的炔基芳基pi共轭桥建构偶极/多极有机金属(长直链型、十字型、星型和树枝状超分子)共轭体系, 3) 多种大pi共轭结构、轴向或径向共轭修饰的卟啉/酞菁及其金属衍生物、不同端位连接方式和合成途径构筑卟啉/酞菁及其衍生物共轭功能化石墨烯/碳纳米管等三类无机-有机二元杂化功能分子材料, 研究与优化这些二元共轭体系在近红外波段的超快三阶非线性光学性能, 在分子水平上探讨这些无机-有机二元杂化功能材料的结构与其近红外三阶非线性光学性能的构效关系, 尝试阐明这些二元共轭体系近红外三阶光学非线性的物理机制和动力学过程，探索面向近红外通讯波段的新型三阶非线性光学材料与器件。

近红外波段(波长在780-3000 nm)非线性光学材料在民用、特别是军事技术领域如激光制导、激光雷达、激光通讯等空间探测领域具有极其重要的应用价值，迫切需要研究和创制高性能、快速响应的新型近红外非线性光学功能材料和器件。.主要研究内容为设计与制备无机-有机杂化近红外非线性光学功能材料，探讨创制：1)多种大Π共轭结构、轴向或径向共轭修饰的卟啉/融合卟啉及其金属衍生物构筑卟啉及其衍生物共轭功能化石墨烯/碳纳米管，2)过渡/主族/镧系金属硼酸盐、碘酸盐、硒酸盐、硫酸盐及硝酸盐及其二元复合物等晶态材料，3)多种共轭有机桥连基团和电子结构特征的金属簇合物构建单元创制过渡金属簇合物-有机框架结构, 以及低维半导体纳米异质结构等几类无机-有机二元杂化功能分子材料, 研究与优化这些二元共轭体系在近红外波段的超快非线性光学性能, 在分子水平上探讨这些二元杂化功能材料的结构与其近红外非线性光学性能的构效关系, 阐明共轭体系近红外光学非线性的物理机制和动力学过程。.重要成果如下：设计与制备了共轭融合卟啉二聚体并构建新型具有近红外非线性吸收的融合卟啉二聚体单壁碳纳米管杂化材料，原位于550 nm处的Q带进一步红移至1048 nm近红外区域，在 800 nm、340 fs激光脉冲下，该杂化材料具有显著增强的 NLO 性能，双光子吸收截面值约为13970 GM；首次将氟代5d0金属八面体引入碘酸盐晶体材料，制备了K5(W3O9F4)(IO3)晶体，该晶体材料在1064和2100 nm处倍频强度是KDP和AgGaS2的11倍和0.5倍，其激光损伤阈值是200.9 MW/cm2 (95 × AgGaS2)；利用化学气相沉积法并通过控制反应温度制备了一种垂直堆叠的单层二硫化钼纳米片与硫化亚铜纳米颗粒的P-N异质结，其有效的电致非线性吸收系数是(3.04 ± 0.34) × 104 cm/GW，是硫化亚铜颗粒的非线性吸收系数两倍。

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