New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials.

ConspectusThe invention of the laser is a pivotal milestone in the evolution of modern science and technology. Second-order nonlinear optical (NLO) crystals, which possess the ability to convert frequencies, have found widespread applications in laser science, information transmission, industrial Internet, and other cutting-edge fields within materials and optics. As modern science and technology continue to advance at a rapid pace, existing ultraviolet (UV) and deep ultraviolet (DUV) NLO crystals struggle to meet the ever-growing demands of various applications. Consequently, the development of novel UV and DUV NLO crystals has become an urgent necessity. For a UV NLO crystal to be considered outstanding in the UV/DUV range, it must exhibit three fundamental yet crucial properties: large second-order NLO coefficients, suitable birefringence, and short UV cutoff edge corresponding to a wide band gap. However, these key factors often conflict with one another, making it challenging to achieve a harmonious balance within a single crystal. It is widely believed that these mutually constrained optical properties are codetermined by microscopic NLO-active units and macroscopic structure features. Therefore, how to design high performance UV NLO-active groups to balance these three key properties is an essential scientifically question and serious challenge. In this Account, we present three strategies for designing high-performance UV NLO-active groups: (1) The "tetrahedron partial substitution" strategy by employing various substituents to replace one or more atoms in the traditional nonpolar tetrahedral groups, might achieve the aim of increasing the polarizability anisotropy and hyperpolarizability of the newly formed polar tetrahedral functional groups, such as from SO to SONH or SOCH groups. (2) The "structure-analogue" strategy to develop a range of organic functional groups exhibiting more strong polarizability anisotropy and hyperpolarizability by using inorganic π-conjugated groups, such as BO and BO groups, as templates. (3) The "two in one" strategy for integrating groups featuring planar triangle configurations and tetrahedrons to create NLO-active functional groups possessing large band gaps, strong hyperpolarizability, and moderate polarizability anisotropy. These three strategies successfully guide us to design and explore various kinds of organic-inorganic composite NLO crystal materials with excellent performances, like Ba(SOCH), M(SONH) (M = Sr, Ba), C(NH)SOF, KLi(HCNO)·2HO, KLi(CHO)·HO, and so on. Finally, we briefly conclude these strategies and propose some prospects for exploring new excellent UV/DUV NLO materials with practical applications. These findings could inspire novel thoughts for researchers designing new UV/DUV NLO materials and providing abundant materials used in UV/DUV regions.