It is challenging to explore deep-ultraviolet (deep-UV) nonlinear optical (NLO) materials that can achieve a subtle balance between deep-UV transparency and high NLO activity. Known are almost exclusively limited borates, except few newly discovered phosphates despite their small activities. Here we report two asymmetric phosphates, RbBa2(PO3)5 (I) Rb2Ba3(P2O7)2 (II), which feature [PO3]∞ chains [P2O7](4-) dimers formed by condensation of [PO4](3-) units, respectively. Remarkably, I achieves...

A new beryllium-free borate Rb3Al3B3O10F has been synthesized and characterized by single-crystal X-ray diffraction. It features a framework structure consisting of alveolate [Al3(BO3)3OF]∞ layers tightly bound via Al-O Al-F bridged bonds, with the in-layer [BO3](3-) groups in nearly coplanar aligned arrangement. This compound is transparent down to 200 nm phase-matchable powder second-harmonic generation efficiency 1.2 times that KH2PO4. Remarkably, it exhibits strong interlayer bonding...

A beryllium-free deep-ultraviolet (deep-UV) nonlinear optical (NLO) material K3Ba3Li2Al4B6O20F is developed mainly by the element substitution of Be for Al and Li from Sr2Be2B2O7 that was considered as one most promising deep-UV NLO materials. preserves structural merits thus exhibits no layering growth tendency possesses properties required applications, including transparency, phase-matchability, sufficiently large second-harmonic generation (1.5 × KH2PO4). Furthermore, it overcomes...

A nonlinear optical phosphate Ba5P6O20 was rationally developed by a tailored synthetic approach based on the use of flexible [P3O10](5-) units. The exhibits very short absorption edge λ=167 nm, which is among shortest known in phase-matchable phosphates. First-principles electronic structure analysis elucidated origin changes properties, and specifically edge, material. Such provides new opportunity to design materials with edges.

It is of great difficulty to obtain deep-UV transparent materials with enhanced second harmonic generation (SHG), mainly limited by the theoretically poor transparency these in spectral region. Here we report a new noncentrosymmetric, phosphate RbNaMgP2O7, which undergoes thermo-induced reversible phase transition (at high temperature 723 K) and correspondingly an evident SHG enhancement up ∼1.5 times. The aroused twist [P2O7]4- dimers deviation from P-O-P equilibrium positions. Theoretical...

Perovskite ferroelectrics with prominent nonlinear optical absorption have attracted great attention in the field of photonics. However, they are traditionally dominated by inorganic oxides and exhibit relatively small coefficients, which hinder their further applications. Herein, we report a new organic–inorganic hybrid bilayered perovskite ferroelectric, (C4H9NH3)2(NH2CHNH2)Pb2Br7 (1), showing an above-room-temperature Curie temperature (∼322 K) notable spontaneous polarization (∼3.8 μC...

The non-π-conjugated sulfate system has long been overlooked as potential deep-UV nonlinear optical (NLO) materials. Here we report two asymmetric anhydrous sulfates, namely, NH4NaLi2(SO4)2 (Ι) and (NH4)2Na3Li9(SO4)7 (Π), which consist of [SO4]2- anions. Their single crystals can be readily grown by a facile evaporation method from water solution. Both sulfates are transparent down to the region. Interestingly, there is large NLO gap between I Π, with phase-matching responses 1.1 0.5 times...

Abstract Perovskite‐type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because their unique effects (PVEs). A new layered perovskite‐type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead ( 1 ), is presented. The material exhibits an exceptional anisotropy bulk PVEs. Upon photoexcitation, superior behaviors created along its inorganic layers, which corner‐sharing PbBr 6 octahedra. Semiconducting...

Abstract Antimony(III) borates with a stereochemical active lone pair remained unknown, although the first antimony borate was reported more than twenty years ago. Now, antimony(III) in closed system is successfully synthesized, namely SbB 3 O 6 . Remarkably, not only exhibits an exceptional linear optical response, that is, birefringence of Δn=0.290 at wavelength 546 nm, which largest among borates, but also has strong nonlinear response 3.5 times larger benchmark KH 2 PO 4 , exceeding...

Abstract Metal‐halide perovskites are recently emerging as the promising alternative for CPL detection owing to their CPL‐sensitive property induced by chiral organics and efficient charge transport of inorganic frameworks. However, most these reported involve high concentrations toxic Pb which will become potential bottleneck further application. Herein, we successfully developed two lead‐free halide double perovskites, [( R )‐β‐MPA] 4 AgBiI 8 (( )‐β‐MPA=( )‐(+)‐β‐methylphenethylammonium,...

Hydrogen-bonded organic frameworks (HOFs) are a rising class of promising proton-conducting materials. However, they always suffer from the inherent contradiction between chemical stability and proton conduction. Herein, inspired by self-assembly lipid bilayer membranes, series aminomethylphosphonic acid-derived single-component HOFs successfully developed with different substituents attached to phosphonate oxygen group. They remain highly stable in strong acid or alkaline water solutions...

Birefringent crystals that can modulate the polarization of light play a significant role in modern optical devices including polarizing microscopes, isolators, and achromatic quarter-wave plates. To date, commercial birefringent are exclusively limited to purely inorganic compounds. Here we report new organic-inorganic hybrid halide, MLAPbBr4 (MLA=melamine), which features (110)-oriented layered perovskite structure. Although 6s2 lone-pair electrons Pb2+ cations stereochemically inert,...

ConspectusSecond-order nonlinear optical (NLO) materials, producing coherent light by the cascaded frequency conversion, are current hot topics in material chemistry and optics, as they play an important role diverse fields, such laser technology, precision measurements, quantum information well future space propulsion. The prerequisite for a second-order NLO is that it must crystallize noncentrosymmetric group, but tends to be centrosymmetric terms of thermodynamical stability. Furthermore,...

Cesium-lead halide perovskites (e.g. CsPbBr3 ) have gained attention because of their rich physical properties, but bulk ferroelectricity remains unexplored. Herein, by alloying flexible organic cations into the cubic , we design first cesium-based two-dimensional (2D) perovskite ferroelectric material with both inorganic alkali metal and cations, (C4 H9 NH3 )2 CsPb2 Br7 (1). Strikingly, 1 shows a high Curie temperature (Tc =412 K) above that BaTiO3 (ca. 393 notable spontaneous polarization...

Developing superior deep-ultraviolet (deep-UV) nonlinear optical (NLO) materials is a great challenge because of the contradiction between deep-UV transparency and enhanced second harmonic generation (SHG), especially for NLO phosphates in which constituent P–O groups have relatively small microscopic SHG coefficients. Here we report new noncentrosymmetric phosphate Cs2LiPO4 (I), whose crystal structure consists [LiPO4]∞ layered structural units with novel honeycomb-like topology. As...

Poor stability has long been a major obstacle to the practical applications of metal–organic framework (MOF) photocatalysts. This problem can be overcome by use structural interpenetration. In this work, modifying Ru metalloligands, we have rationally designed two Ru–polypyridine based MOFs (with non-interpenetrated and interpenetrated structures, respectively), both which exhibit similar photocatalytic activities for CO2 photoreduction. Remarkably, Ru-MOF possesses good durability...

Unique 3D hierarchical flower-like metal–organic nanostructures have been reported, which can act as stable and effective heterogeneous photocatalysts for visible-light driven CO₂photoreduction.

Structures composed of SiOxF6-x (x = 1, 2, 3, 4, 5) or SiOxF4-x 3) species have thus far been observed in only a few compounds, and their functional properties are completely unknown silicate chemistry. By introducing the least electronegative element, cesium, most fluorine, into silicophosphate system, we successfully designed first noncentrosymmetric fluorooxosilicophosphate with Si-F bonds, CsSiP2O7F, whose structure consists an unprecedented SiP2O10F moiety containing hexacoordinate...

A new noncentrosymmetric borate CsZn2B3O7 was synthesized by the solid-state reaction techniques. The crystals were obtained flux method and are of block shape without layering tendency. Single-crystal X-ray diffraction analysis reveals that crystal structure is composed [Zn2BO5]∞ two-dimensional layers bridged [B3O6]3– groups to form a three-dimensional framework with one-dimensional channels occupied Cs+ cations along c axes. Thermal indicates melts incongruently. UV–visible–near-IR...

Abstract Nitrates have long been ignored for practical uses as nonlinear optical (NLO) materials because they are usually very easy to dissolve in water; despite this, the π‐conjugated [NO 3 ] − is among most desirable NLO‐active structural units. The cooperation of three chromophores, namely, Bi O 6 OH short chains with 6s 2 lone pair electrons, distorted TeO octahedra d 10 and triangles, generates a new nitrate NLO material, OH(NO ) , which exhibits an enhanced phase‐matchable response...