Metalation of metal-organic frameworks: fundamentals and applications.

Metalation of metal-organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization for pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in a wide range of applications. In this review, we focus on the research progress in the metalation of metal-organic frameworks during the last five years, spanning the design principles, synthetic strategies, and potential applications. Based on the crystal engineering principles, a minor change in the MOF composition through metalation would lead to leveraged variation of properties. This review starts from the general strategies established for the incorporation of metal species within MOFs, followed by the design principles to graft the desired functionality while maintaining the porosity of frameworks. Facile metalation has contributed a great number of bespoke materials with excellent performance, and we summarize their applications in gas adsorption and separation, heterogeneous catalysis, detection and sensing, and energy storage and conversion. The underlying mechanisms are also investigated by state-of-the-art techniques and analyzed for gaining insight into the structure-property relationships, which would in turn facilitate the further development of design principles. Finally, the current challenges and opportunities in MOF metalation have been discussed, and the promising future directions for customizing the next-generation advanced materials have been outlined as well.

Al8 Cluster-Based Metal Halide Frameworks: Balancing Singlet-Triplet Excited States to Achieve White Light and Multicolor Luminescence.

Luminescent metal clusters have attracted great interest in current research; however, the design synthesis of Al clusters with color-tunable luminescence remains challenging. Herein, an [Al8 (OH)8 (NA)16 ] (Al8 , HNA = nicotinic acid) molecular cluster with dual luminescence properties of fluorescence and room-temperature phosphorescence (RTP) is synthesized by choosing HNA ligand as phosphor. Its prompt photoluminescence (PL) spectrum exhibits approximately white light emission at room temperature. Considering that halogen atoms can be used to regulate the RTP property by balancing the singlet and triplet excitons, different CdX2 (X- = Cl- , Br- , I- ) are introduced into the reactive system of the Al8 cluster, and three new Al8 cluster-based metal-organic frameworks, {[Al8 Cd3 Cl5 (OH)8 (NA)17 H2 O]·2HNA}n (CdCl2 -Al8 ), {[Al8 Cd4 Br7 (OH)8 (NA)16 CH3 CN]·NA·HNA}n (CdBr2 -Al8 ) and {[Al8 Cd8 I16 (OH)8 (NA)16 ]}n (CdI2 -Al8 ) are successfully obtained. They realize the color tunability from blue to yellow at room temperature. The origination of fluorescence and phosphorescence has also been illustrated by structure-property analysis and theoretical calculation. This work provides new insights into the design of multicolor luminescent metal cluster-based materials and develops advanced photo-functional materials for multicolor display, anti-counterfeiting, and encryption applications.

A Noncentrosymmetric Metal-Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent-Linkage.

Organic-inorganic hybrid linear and nonlinear optical (NLO) materials have received increasingly wide spread attention in recent years. Herein, the first hybrid noncentrosymmetric (NCS) borophosphate, (C5H6N)2B2O(HPO4)2 (4PBP), is rationally designed and synthesized by a covalent-linkage strategy. 4-pyridyl-boronic acid (4 PB) is considered as a bifunctional unit, which may effectively improve the optical properties and stability of the resultant material. On the one hand, 4 PB units are covalently linked with PO3(OH) groups via strong B-O-P connections, which significantly enhances the thermal stability of 4PBP (decomposition at 321, vs lower 200 °C of most of hybrid materials). On the other hand, the planar π-conjugated C5H6N units and their uniform layered arrangements represent large structural anisotropy and hyperpolarizability, achieving the largest birefringence (0.156 @ 546 nm) in the reported borophosphates and a second-harmonic generation response (0.7 × KDP). 4PBP also exhibits a wide transparency range (0.27-1.50 µm). This work not only provides a promising birefringent material, but also offers a practical covalent-attachment strategy for the rational design of new high-performance optical materials.

Near-Full-Spectrum Emission Realized in a Single Lead Halide Perovskite across the Visible-Light Region.

The engineering of tunable photoluminescence (PL) in single materials with a full-spectrum emission represents a highly coveted objective but poses a formidable challenge. In this context, the realization of near-full-spectrum PL emission, spanning the visible light range from 424 to 620 nm, in a single-component two-dimensional (2D) hybrid lead halide perovskite, (ETA)2PbBr4 (ETA+ = (HO)(CH2)2NH3+), is reported, achieved through high-pressure treatment. A pressure-induced phase transition occurs upon compression, transforming the crystal structure from an orthorhombic phase under ambient conditions to a monoclinic structure at high pressure. This phase transition driven by the adaptive and dynamic configuration changes of organic amine cations enables an effective and continuous narrowing of the bandgap in this halide crystal. The hydrogen bonding interactions between inorganic layers and organic amine cations (N-H…Br and O-H…Br hydrogen bonds) efficiently modulate the organic amine cations penetration and the octahedral distortion. Consequently, this phenomenon induces a phase transition and results in red-shifted PL emissions, leading to the near-full-spectrum emission. This work opens a possibility for achieving wide PL emissions with coverage across the visible light spectrum by employing high pressure in single halide perovskites.

Gradual Size Enlargement of Aluminum-Oxo Clusters and the Photochromic Properties.

Metallic clusters, assembled by functional motifs, possess the attribute of regulating the properties by changing inorganic and organic components. In this work, a series of aluminum-oxo clusters, [Al6O(dmp)4(Hdmp)2]·2iPrOH [Al6-1, H3dmp = 2,2-bis(hydroxymethyl)propionic acid], [Al6(H2thmmg)6]·2DMF·2H2O [Al6-2, H5thmmg = N-tris(hydroxymethyl)methylglycine], [Al8(OH)4(NAP-OH)12(MeO)7(MeOH)]Cl·7MeCN·3MeOH (Al8, HNAP-OH = 3-hydroxy-2-naphthoic acid), and [Al10(NA)10(MeO)20] (Al10, HNA = nicotinic acid), were obtained based on different carboxylic acids, realizing metallic ring size enlargement from 5.91 to 9.32 Å. They all exhibit good chemical stability. Importantly, the Al8 cluster displays obvious photochromic behavior from pale yellow to orange yellow, originating from the generation of photoinduced radicals in the metal-assisted ligand-ligand electron transfer process of 3-hydroxy-2-naphthoic acid (HNAP-OH). This work enriches the metal ring cluster chemistry and reports the example of the aluminum-oxo cluster-based photochromic material, developing a novel system of photochromic materials.

Multicolor Phosphorescence Modulated by Excitation and Temperature in Zn-Based Coordination Polymers.

Color-tunable room-temperature phosphorescence (RTP) with potential in many fields is of great importance but extremely challenging. It is necessary to comprehend the correlation between the molecular structure and property to design and synthesize such materials. Metal-organic coordination polymers (CPs) with good predesignability and precise structure have become a platform to construct RTP materials. Herein, three zinc-based CPs containing halogen and a flexible tetradentate ligand are synthesized. All of these CPs present two constant emission regions and an excitation-dependent emission region. Structure-property analysis shows that these emissions originate from isolated chromophores and dimerized chromophores as well as various charge transfers. The phosphorescence colors of these CPs can be modulated by excitation and temperature. This study provides a novel strategy to construct multicolor and multiresponsive RTP materials based on metal-organic coordination polymers.

Sb4O3(TeO3)2(HSO4)(OH): An Antimony Tellurite Sulfate Exhibiting Large Optical Anisotropy Activated by Lone Pair Stereoactivity.

A new birefringent crystal of Sb4O3(TeO3)2(HSO4)(OH) was achieved by incorporating two stereochemically active lone pair (SCALP) cations of Sb(III) and Te(IV) into sulfates simultaneously. The Sb3+ and Te4+ ions display highly distorted coordination environments due to the SCALP effect. Sb4O3(TeO3)2(HSO4)(OH) displays a 3D structure composed of [Sb4O3(TeO3)2(OH)]∞+ layers bridged by [SO3(OH)]- tetrahedra. It possesses a large birefringence and a wide optical transparent range, making it a new UV birefringent crystal. First-principles calculation analysis suggests that the synergistic effect of the cooperation of SCALP effect of Sb3+ and Te4+ cations make a dominant contribution to the birefringence. The work highlights that units with SCALP cations have advantages in generating large optical anisotropy and are preferable structural units for designing novel birefringent materials.

Hybrid Photochromic Lanthanide Phosphonate with Multiple Photoresponsive Functionalities.

Hybrid photochromic materials (HPMs) with specific photoresponsive functionality have applications in many fields. The photoinduced electron-transfer (ET) strategy has been proved to be effective in the synthesis of HPMs with diverse photomodulated properties. The exploitation of new electron acceptors (EAs) is meaningful for promoting the development of HPMs. In this work, we introduced a rigid tetraimidazole derivative, 3,3,5,5-tetra(imidazol-1-yl)-1,1-biphenyl (TIBP) as a potential EA, into a metal-diphosphonate (1-hydroxyethylidene-1,1-diphosphonic acid, H4-HEDP) system to explore HPMs and finally obtained a hybrid metal phosphonate (H4-TIBP)0.5·[Dy(H-HEDP) (H2-HEDP)]·H2O (1). 1 features anionic chains composed of diphosphonate and Dy3+ ions. The extra charge is balanced by protonated TIBP cations, which exist in the void of adjacent chains and form H-bonds with Ophosphonate (N-H···O). Upon photostimulation with a Xe lamp (300 W), the crystalline sample 1 exhibited coloration by changing from colorless to pale yellow because of the presence of photoinduced radicals that originated from the ET from Ophosphonate to NTIBP. Along with the coloration, photomodulated fluorescence, magnetism, and proton conductivity were also detected in the photoactivated samples. Different from the reported HPMs based on polypyridine derivatives and photoactive species such as pyridinium and naphthalimide derivatives as EAs, our study provides a new category of EA units to yield HPMs with fascinating photoresponsive functionality via the assembly of polyimidazole derivatives and phosphonate-based supramolecular building blocks.

Photoactive Anthracene-9,10-dicarboxylic Acid for Tuning of Photochromism in the Cd/Zn Coordination Polymers.

Electron transfer photochromic materials with photo-triggered radicals have received huge interest from chemists due to their potentialities in anticounterfeiting, displays, energy conversion, and information storage. However, utilizing the sole carboxylic acid to synthesize novel electron transfer photochromic species is still confronted with huge challenges. Herein, an acentric three-dimensional network Cd2(ADC)2(DMF)2(H2O) (1; ADC = anthracene-9,10-dicarboxylate; DMF = N,N-dimethylformamide) and a two-dimensional layer Zn(ADC)(H2O)·DMA·H2O (2; DMA = N,N-dimethylacetamide) were synthesized and characterized via a photoactive H2ADC ligand. Both compounds exhibited electron transfer photochromism with the formation of radical photoproducts at the solid state, which was revealed by IR, UV-Vis absorption, photoluminescence and electron spin resonance spectra, and magnetic susceptibility measurements. Density functional theory calculations for 1 showed that the coloration process is a metal-assisted ligand-to-ligand electron transfer process between adjacent ADC molecules, and photogenerated stable radicals are delocalized over the ADC components. Compared with 1, the shorter distances between ADC components via coordination bonds promoted 2 to exhibit a higher coloration efficiency and larger quantity of photogenerated radicals. Furthermore, both compounds showed unexpected radical-actuated photochromism in aqueous solution. This work showed that the carboxylic acid ligands, without viologen acceptors, could construct the electron transfer photochromic complexes, showing a novel kind of ligand for the design of hybrid photochromic materials.

Dual-Ligand-Oriented Design of Noncentrosymmetric Complexes with Nonlinear-Optical Activity.

When the N- and O-donor ligands are combined as coligands, two noncentrosymmetric (NCS) complexes of [Ni(p-bdc)(tipa)(H2O)2]2·H2O (1) and Ni(npdc)(tipa)H2O (2) [tipa = tris[4-(1H-imidazol-1-yl)phenyl]amine, p-H2bdc = 1,4-benzenedicarboxylic acid, and H2npdc = 2,6-naphthalenedicarboxylic acid] were achieved under solvothermal conditions. For both structures, N-donor ligands are responsible for the generation of a layered structure, while the O-donor ligands are hung on the layers and are responsible for enhancing the polarity, giving rise to the NCS structures. Because of the different connection modes between the metal centers and different carboxylate ligands (p-bdc2- in 1 and npdc2- in 2), 1 and 2 show some structural differences. The p-bdc2- ligands in 1 are suspended on the upper and lower sides of the [Ni(tipa)]n layers, while all of the npdc2- ligands in 2 hang on one side of the [Ni(tipa)]n layers and point in the same direction, which makes the two NCS complexes show phase-matchable behavior with different second-harmonic-generation (SHG) responses of about 0.9 and 1.5 times that of KH2PO4 (KDP), respectively. Theoretical studies reveal that charge transfers between Ni2+ and carboxylate ligands make the dominant contribution to the optical properties. It is expected that a dual-ligand strategy may guide the design of novel superior-performing NCS complexes.

Coordinate Anchoring of Mixed Luminophores in Two Isostructural Hybrid Layers to Achieve Tunable Room-Temperature Phosphorescence.

Room-temperature phosphorescence (RTP) materials have widespread applications in biological imaging, anticounterfeiting, and optoelectronic devices. Because of the predesignability of metal-organic complexes (MOCs), the RTP materials based on MOC systems have received huge attention from researchers. The coordinate anchoring of luminophores to enhance the rigidity of organic molecules and restrict the nonradiative transition offers opportunities for generating MOC materials with captivating RTP performance. Hitherto, most of the MOC-based RTP materials feature a single luminophore ligand. The development of new MOC systems with RTP functionality is still challenging. Herein, we use the mixed-ligand synthetic strategy to produce isostructural MOCs, [Zn(TIMB)(X2-TPA)]·H2O (1, X = Cl; 2, X = Br; TIMB = 1,3,5-tris(2-methyl-1H-imidazol-1-yl)benzene; H2-X2-TPA = 2,5-dichloroterephthalic and 2,5-dibromoterephthalic acid), and modulate the RTP properties of resultant products via the synergy of coordinate anchoring and substitution synthesis. 1 and 2 feature similar coordination layers composed of neutral TIMB and anionic X2-TPA2- ligands, which provide a good structural model to tune the RTP performances of final products via substitution synthesis. Different from the reported RTP materials based on MOC systems, our study provides a general way to build and modulate MOC-based RTP materials with the assistance of coordinate anchoring and substitution synthesis strategies.

Ultrathin Two-Dimensional Polyoxometalate-Based Metal-Organic Framework Nanosheets for Efficient Electrocatalytic Hydrogen Evolution.

The rational design of 2D polyoxometalate-based metal-organic framework (POMOF) nanosheets on a conductive substrate as a self-supporting electrode is highly attractive but a great challenge. Herein is the first demonstration of POMOF nanopillar arrays consisting of 2D nanosheets as a self-supported electrode for the hydrogen evolution reaction (HER) in acidic conditions. Single-crystal X-ray analysis reveal that our as-prepared 2D [Co2(TIB)2(PMo12O40)]·Cl·4H2O [named CoMo-POMOF; TIB = 1,3,5-tris(1-imidazoly)benzene] crystalline materials are connected by Co-α-Keggin polymolybdate units act as secondary building blocks and TIB as the organic ligands. The 2D CoMo-POMOF nanosheets were successfully arrayed on a conductive nickel foam substrate by a facile CoO nanorod template-assisted strategy. Remarkably, the CoMo-POMOF nanopillar arrays demonstrate superior electrocatalytic performance toward the HER with an overpotential of 137 mV and Tafel slope of 59 mV dec-1 at 10 mA cm-2, which are comparable to those of state-of-the-art POMOF-based electrocatalysts. Density-functional theory (DFT) calculations demonstrate that the exposed bridging oxygen active sites (Oa) of Co-α-Keggin polymolybdate units in CoMo-POMOF optimize the Gibbs free energy of H* adsorption (ΔGH* = -0.11 eV) and increase the intrinsic HER activity.

Large Room Temperature Magnetization Enhancement in a Copper-Based Photoactive Metal-Organic Framework.

The tris(pyridin-4-yl)amine ligand was found to exhibit a radical-actuated coloration phenomenon, and a novel copper-based color-changeable metal-organic framework (MOF) was synthesized via this photoactive ligand. After light irradiation, the photogenerated stable radicals in this framework induced increasing amplitude of magnetization (32%) at room temperature, being the largest enhancement among radical-based photochromic systems.

Decorating Metal Nitrate with a Coplanar Bipyridine Moiety: A Simple and General Method for Fabricating Photochromic Complexes.

As a significant class of photochromic materials, crystalline hybrid photochromic materials (CHPMs) have attracted widespread attention of researchers because of their possibilities for generating other photoresponsive properties and advantages in understanding the underlying relationship between structure and photoresponsive performance. The predesign of suitable ligands plays a major role in generating desirable CHPMs. Hitherto, most CHPMs have been built from photodeformable or photoresponsive tectons. However, the synthesis of these ligands is usually time-consuming and expensive, and this greatly restricts their large-scale preparation and practical application. Therefore, it is necessary to explore new families of CHPMs besides the existing CHPMs. Herein, a simple and general method for constructing CHPMs by decorating metal nitrate with a coplanar bipyridine moiety, namely 1,10-phenanthroline (phen), is reported. The resulting products exhibit photocoloration in response to Xe-lamp irradiation. The electron transfer (ET) from the coplanar NO3 - species (as π-electron donors, π-EDs) to coplanar phen moieties (as π-electron acceptors, π-EAs) is responsible for the resulting photochromism. The influence of the coordination environment and central metal ion on the photochromism was also studied. This work demonstrates that the introduction of coplanar organic tectons as π-EAs to metal nitrates as π-EDs with the collaboration of ET and coordination-assembly strategies is a simple and general method to manufacture CHPMs.

Quadruple Photoresponsive Functionality in a Crystalline Hybrid Material: Photochromism, Photomodulated Fluorescence, Magnetism and Nonlinear Optical Properties.

As promising photoresponsive materials and potential smart materials, hybrid photochromic materials (HPMs), especially for crystalline HPMs (CHPMs), have been broadly explored for their potential in inheriting the merits of each constituents, and intriguing photomodulated functionality. Hitherto, the photoresponsive functionality in explored CHPMs mainly concentrate on dyad combination. By contrast, triple or quadruple photoresponsive properties are very rare because of the limited compatibility of multiple photoresponsive functionality in a single system. In this work, the electron-transfer (ET) and crystal engineering strategies were utilized to predesign CHPMs with multiple photoresponsive properties via the collaboration of paramagnetic metal ion (Dy3+ ), electron-donor (ED) ligand (benzene-1,2,3-tricarboxylic acid, H3 BTA) and electron-acceptor (EA) ligand (1,10-phenanthroline, phen). The resulting complex [Dy(BTA)(phen)2 ]⋅2H2 O (1) shows hybrid chain with the intrachain Dy3+ ions bridged and chelated by tricarboxylate and phen ligands, respectively. After photostimuli, the ET between tricarboxylate and phen results in photogenerated radicals and the resultant quadruple photoresponsive properties. Considering the abundant resources of paramagnetic metal ions, ED- and EA-ligands, this work provides a general method to construct CHPMs with multiple photoresponsive performances via the collaboration of each unit under the guidance of ET and crystal engineering strategies.

The Tri(imidazole)-Derivative Moiety: A New Category of Electron Acceptors for the Design of Crystalline Hybrid Photochromic Materials.

The intermarriage of neutral and tripodal imidazole ligand, tris(4-(1H-imidazol-1-yl)phenyl)amine (TIPA), with zinc phosphite yields two hybrid phosphites, [Zn2 (HPO3 )2 (TIPA)]⋅2 H2 O (1) and [Zn3 (HPO3 )3 (TIPA)]⋅6 H2 O (2). Compound 1 has a hybrid sheet with neutral zinc-phosphite chains as supramolecular building blocks (SBBs), whereas 2 exhibits a 3D hybrid architecture with other neutral zincophosphite chains as supramolecular building blocks. The structural discrepancy between 1 and 2 is mainly due to the distinct linkage modes between organic TIPA ligands and inorganic zincophosphite chains. Interestingly, compounds 1 and 2 feature fast photochromism in response to UV light irradiation under ambient conditions. The discrepancy of photochromic performance between 1 and 2 is mainly due to the different geometrical configuration of the TIPA ligand. Different to majority of reported hybrid photochromic compounds driven by photochromic active units, the photochromism in 1 and 2 is derived from the electron transfer (ET) between phosphite and non-photochromic triimidazole-derivative ligand TIPA. Compared with the widely explored nonphotochromic polypyridine-derivative as electron acceptors (EAs), our work provides a new EA model for the design of hybrid photochromic materials based on the ligand-to-ligand ET mechanism. A multiple anti-counterfeiting application based on 1 and 2 was investigated.

Sb6 O7 (SO4 )2 : A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second-Harmonic-Generation Response Activated by SbIII Lone-Pair Stereoactivity.

The stereochemical activity of lone pairs (SCALP) in a cation favors the formation of acentric materials and can enhance the second-harmonic-generation (SHG) response and/or the birefringence. By introducing functional SbIII into sulfates, an anhydrous sulfate of Sb6 O7 (SO4 )2 (1) is explored. Sb3+ cations are in seesaw configurations and in-phase aligned in a 3D asymmetric dense structure. Compound 1 exhibits an enhanced phase-matching SHG response, a moderate birefringence, a wide transparency window, and considerable environmental stabilities, which result in it being a promising UV nonlinear optical (NLO) material. Theoretical studies reveal that the stereoactive lone pairs on Sb3+ cations make the predominant contribution to the SHG effect. This work will attract more interest from scientists for research into SCALP-cation-based NLO materials.

Two Photochromic Complexes Assembled by a Nonphotochromic Ligand: Photogenerated Radical Enhanced Room-Temperature Phosphorescence.

Stimulating tunable room-temperature phosphorescence (RTP) is still a challenge in photochromic systems, which is vital for multifunctional coordination materials. Herein, we synthesized two new photochromic chain complexes through self-assembly of the nonphotochromic 1,3,5-tris(4-pyridyl)benzene ligand, diphosphonate, and Ln(III) ions (1 for Ln(III) = Dy and 2 for Ln(III) = Gd). Both compounds showed fast photoresponses with the color turning from yellow to dark gray with a reversible decoloration by heating or storage in the dark. The electron transfer photochromic behavior with the generated stable radicals was further confirmed by the room-temperature UV-vis and electron paramagnetic resonance spectra. Furthermore, via tuning the generation and disappearance of stable radicals, reversible room-temperature fluorescence and phosphorescence for both compounds were switched by light irradiation and a thermal treatment, with an enhanced intensity for RTP and a decrease in fluorescence during the duration of Xe-lamp light irradiation. This work provides a new strategy that photogenerated radicals could promote and enhance RTP properties in functional materials.

Conjugated-Polypyridine-Derivative-Derived Semiconductive Iodoplumbates with Tunable Architectures and Efficient Visible-Light-Induced Photocatalytic Property.

By mediation of the pH values, three novel inorganic-organic iodoplumbate hybrids, [Me3TPT][Pb3I9] [1; Me3TPT = trimethyl-2,4,6-tris(4-pyridyl)-1,3,5-triazine], [Me3TPT]2[Pb9I24] (2), and [Me3TPT]2[Pb19I44] (3), have been achieved under solvothermal conditions. The large conjugated in situ N-alkylation polypyridine derivatives act as structure-directing agents and electron acceptors, making the materials feature adjustable structural variations with 0D, 1D, and 2D structures and a potential semiconductive performance with narrow energy gaps (1.72, 1.80, and 1.78 eV for 1-3, respectively), which result in their efficient photocatalytic activity under visible-light irradiation. Theoretical calculation reveals that the conjugated organic moieties greatly contribute to the conduction band, leading to narrow band gaps. It is expected that the work will contribute to the exploitation of novel semiconducting halometallates by employing conjugated organic species as structure-directing agents.

Linear and Nonlinear Optical Properties of Centrosymmetric Sb4O5SO4 and Noncentrosymmetric Sb4O4(SO4)(OH)2 Induced by Lone Pair Stereoactivity.

Introducing stereochemically active lone-pair Sb3+ cations into sulfates, two three-dimensional (3D) antimony-sulfates, Sb4O5SO4 (1) and Sb4O(SO4)(OH)2 (2), were achieved under moderate hydrothermal conditions. Both structures are constructed by tetranuclear-{Sb4}-clusters-based layers and SO4 tetrahedra. However, owing to the different packing patterns of the layers, they display different characteristics: 1 exhibits a centrosymmetric structure while 2 possesses a noncentrosymmetric structure. UV-vis spectra show that they possess wide band gaps. Sb4O(SO4)(OH)2 is nonlinear optical (NLO) active with a second-harmonic generation (SHG) response of ∼1.2 times of KH2PO4, together with the phase-matchable capacity, endowing it a promising UV NLO material. The first-principle calculations were performed to elucidate the structure-property relationships. The results indicate that the lone pair stereoactivity of Sb3+ provides the large contribution to the macroscopic SHG effect.