Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.

Emerging Multifunctional Metal-Organic Framework Materials.

The term nonlinear optics (NLO) was coined to describe the nonlinear relationship between dielectric polarization P and electric field E in optical media. NLO is a cornerstone of the emerging field of photonics, in which photons instead of electrons are used for signal transmission and processing. The vision of photonic signal transmission, processing, and storage has attracted a great deal of attention from both the engineering and the scientific communities because of its great impact in many of the existing and future information technologies. The first step toward realization of these revolutionary technologies is to develop tools to manipulate photons. For example, it is desirable to develop materials with the ability to alter the frequency of light, to amplify light signal, and to modulate light intensity or phase factors. NLO phenomena can be the key to achieving these important functions. One of the most common NLO behaviors is second-harmonic generation (SHG), in which a NLO material mediates the “adding-up” of two photons to form a new one with twice the frequency. The SHGphenomenonwas first demonstrated by Franken et al. in 1961. In their pioneering work, a laser beam with a wavelength of 694.2 nm was irradiated through a quartz crystal and an output ultraviolet radiation with a wavelength of 347.1 nm (double frequency) was detected. After this discovery, numerous nonlinear optical phenomena have been studied and a number of NLO-active materials have been developed. Second-harmonic generation can be quantitatively described by the second-order nonlinear optical susceptibility χ, a third-rank tensor with 27 components. The tensor elements are related to each other tomeet the requirements of both inherent and structural symmetries, which greatly reduces the number of independent components of the susceptibility tensor. Only crystals in noncentrosymmetric crystal classes can have nonvanishing χ. Moreover, for material crystallizing in the noncentrosymmetric 422, 622, and 432 crystal classes, the second-order NLO response might also vanish due to structural symmetry as well as Kleinman’s symmetry. Many inorganic compounds crystallize in noncentrosymmetric space groups and have been found to be SHG active. Some important examples are potassium dihydrogen phosphate (KDP = KH2PO4), lithium niobate (LiNbO3), and barium sodium niobate (Ba2NaNb5O15). 7 New inorganic compounds have been explored for NLO applications including but not limited to metal borates 12 and metal oxides. Recent structural studies on the inorganic systems have led to a better understanding of crystal growth/packing, paving the way for potentially manipulating their crystallization tendency to form noncentrosymmetric structures. Since the 1970s molecular NLO materials, including organic, organometallic, and inorganic complexes, have been of increasing interest to synthetic chemists. 19 The existing library of organic compounds was first screened, and the urea crystal has become a SHG standard because of its high SHG efficiency and usual availability. In a microscopic view, the second-order NLO susceptibility χ is related to the first hyperpolarizability β of a molecule. According to the classical two-level model, β is enhanced by a large transition moment and a large dipole moment difference between the ground and the charge transfer excited state. A donor acceptor type of molecule often possesses both a large transition moment and a large excited state dipole moment. As a result, most of the organic SHG chromophors belong to this category. However, most of the molecules with large β values also possess a large dipole moment, which induces formation of centrosymmetric assemblies of molecules due to dipole dipole interactions. One of the methods to avoid the centrosymmetric alignment of molecular dipoles is to trap them inside the channels of asymmetric porous host structures. 28 Other methods include formation of poled polymers in which the required asymmetry is imposed by the external electric field 35 and the Langmuir Blodgett (LB)

Rational synthesis of noncentrosymmetric metal-organic frameworks for second-order nonlinear optics.

The discovery of new nonlinear optical (NLO) materials for coherent light generation in the deep-ultraviolet (DUV, wavelength below 200 nm) region is essential for the development of laser technologies. Herein, we report a new material CsB4O6F (CBF), which combines the superior structural properties of two well-known NLO materials, beta-BaB2O4 (BBO) and KBe2BO3F2 (KBBF). CBF exhibits excellent DUV optical properties including a short cutoff edge (155 nm), a large SHG response (approximate to 1.9 X KDP), and a suitable birefringence that enables frequency doubling down to 171.6 nm. Remarkably, CBF melts congruently and shows an improved growth habit. In addition, our rational design strategy will contribute to the discovery of DUV NLO materials.

CsB4O6F: A Congruent-Melting Deep-Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units

Materials chemistry and the pursuit of new compounds through exploratory synthesis are having a strong impact in many technological fields. The field of nonlinear optics is directly impacted by the availability of enabling materials with high performance. Nonlinear optical (NLO) phenomena such as second harmonic and difference frequency generation (SHG and DFG, respectively) are effective at producing a coherent laser beam in difficult to reach frequency regions of the electromagnetic spectrum. Such regions include the infrared (IR), far-infrared, and terahertz frequencies. High performance NLO crystals are critical for applications utilizing these coherent light sources, and new materials are continuously sought for better conversion efficiency and performance. The class of metal chalcogenides is the most promising source of potential NLO materials with desirable properties particularly in the IR region where most classes of materials face various fundamental challenges. We review the recent developments...

Metal Chalcogenides: A Rich Source of Nonlinear Optical Materials

The generation of intense coherent deep-UV light from nonlinear optical materials is crucial to applications ranging from semiconductor photolithography and laser micromachining to photochemical synthesis. However, few materials with large second harmonic generation (SHG) and a short UV-cutoff edge are effective down to 200 nm. A notable exception is KBe2BO3F2, which is obtained from a solid-state reaction of highly toxic beryllium oxide powders. We designed and synthesized a benign polar material, Ba4B11O20F, that satisfies these requirements and exhibits the largest SHG response in known borates containing neither lone-pair-active anions nor second-order Jahn-Teller-active transition metals. We developed a microscopic model to explain the enhancement, which is unexpected on the basis of conventional anionic group theory arguments. Crystal engineering of atomic displacements along the polar axis, which are difficult to attribute to or identify within unique anionic moieties, and greater cation polarizabilities are critical to the design of next-generation SHG materials.

Designing a deep-ultraviolet nonlinear optical material with a large second harmonic generation response.

Hydrothermal synthesis, growth, and properties of a new chloride iodate

Non-centrosymmetric BaNaP3O9 with a short deep-ultraviolet cutoff edge

Synthesis, Structure, and Properties of Nonlinear Optical Crystal Na2SiF6

For phosphate nonlinear optical (NLO) materials, how to improve their small birefringence is confronted with a great contradiction of their weak optical anisotropy of tetrahedral PO4 groups. Herein, by introducing La3+ with a closed-shell structure and Cd2+ with a d10 electronic configuration, two NLO materials with a large birefringence, namely, La(PO3)3 (0.040@1064 nm) and β-Cd(PO3)2 (0.059@1064 nm), have been synthesized by a high-temperature solution method. In particular, for β-Cd(PO3)2, it possesses the largest birefringence among the known deep-ultraviolet (DUV) phosphates to date, which is attributed to cooperative effects of strong covalence of Cd–O groups and P–O pseudolayers similar to those of a plane. Meanwhile, β-Cd(PO3)2 exhibits the shortest cutoff edge (<190 nm) among the reported Cd-based inorganic compounds and realizes a balance between DUV transparence and a large birefringence. This insight provides a new opportunity to design high-performance NLO materials using metal phosphates. 

Zhaohui Chen

Papers

Hydrothermal synthesis, growth, and properties of a new chloride iodate

Non-centrosymmetric BaNaP3O9 with a short deep-ultraviolet cutoff edge

Synthesis, Structure, and Properties of Nonlinear Optical Crystal Na2SiF6

Two Metal Phosphate Nonlinear Optical Materials Simultaneously Exhibiting Ultraviolet Transparence and a Large Birefringence

A2BBi2(PO4)2(P2O7) (A = K, Rb, B = Pb, Cd): the Effect of Cation Sizes on Structural Evolution