Semiconductive Coordination Polymer with Multi-Channel Charge Transfer for High-Performance Direct X-ray Detection.

Coordination polymers (CPs) are promising for direct X-ray detection and imaging owing to higher designability and outstanding stability, however, it remains a challenge to achieve highly X-ray detection performance, particularly both high sensitivity and low detection limit at the same operating voltage. Herein, we construct a new conjugated CP {[Co(BPTTz)(DIPA)] ⋅ DMA} (1, BPTTz=2,5-bis(pyridine-4-yl)thiazolo[5,4-d]thiazole, HDIPA=2,5-diiodoterephthalic acid, DMA=N, N'-dimethylacetamide), with multi-channel charge transfer by regulating the linker mediated electronic-state, which reduces carrier losses resulting from recombination or quenching, enhances the efficiency of charge separation and transfer, thus further optimizes X-ray detection performance. The semiconductor prepared based on this strategy achieves record values including the highest mobility-lifetime product (μτ, 8.

Structure-Induced Energetic Coordination Compounds as Additives for Laser Initiation Primary Explosives.

Laser ignition of primary explosives presents more reliable alternative to traditional electrical initiation methods. However, the commercial initiator lead azide (LA) requires a high-power density laser to detonate, with the minimum laser initiation energy (E) of 2402 mJ. Currently, the laser-ignitable metal complex-based igniters still suffer from weak detonation capabilities and high E values.

Achieving Phase-Matching in Nonlinear Optical Materials CsMInS (M = Cd/In, Hg/In) by the Incorporation of Unprecedented Trigonal Planar MS Motifs.

The trigonal planar unit possesses significant hyperpolarizability and polarizability anisotropy, which makes it useful for optimizing nonlinear optical (NLO) materials, however, chalcogenide with this unit has seldom been reported. In this work, a novel approach is introduced by integrating the unprecedented trigonal planar MS (M = Cd/In, Hg/In) motifs into the nearly optically isotropic tetrahedral units, resulting in two novel chalcogenides CsMInS (M = Cd/In, 1; Hg/In, 2). Notably, structures 1 and 2 feature nearly planar triangular units at the center, encircled by three trimers, further interconnecting each other to create 3D frameworks.

Salt-inclusion chalcogenides with d-orbital components: unveiling remarkable nonlinear optical properties and dual-band photoluminescence.

Metals containing d-orbitals are typically characterized by strong deformation and polarization, yet they tend to induce narrow bandgaps that render them little-appreciated by high-power nonlinear optical (NLO) crystals. Incorporating highly electropositive polycations into d-orbital-containing chalcogenides to modify them into salt-inclusion chalcogenides (SICs) that are competitive in NLO materials, is a viable solution to this predicament. In the present work, two isostructural SICs [KCl][MGaS] (M = Mn, 1; Hg, 2) are successfully synthesized by the high-temperature molten-salt growth method.

HgBr: an easily growing wide-spectrum birefringent crystal.

Birefringent materials are of great significance to the development of modern optical technology; however, research on halide birefringent crystals with a wide transparent range remains limited. In this work, mercuric bromide (HgBr) has been investigated for the first time as a promising birefringent material with a wide transparent window spanning from ultraviolet (UV) to far-infrared (far-IR) spectral regions (0.34-22.

Thermally Activated Delayed Fluorescence (TADF)-active Coinage-metal Sulfide Clusters for High-resolution X-ray Imaging.

The study of facile-synthesis and low-cost X-ray scintillators with high light yield, low detection limit and high X-ray imaging resolution plays a vital role in medical and industrial imaging fields. However, the optimal balance between X-ray absorption, decay lifetime and excitonic utilization efficiency of scintillators to achieve high-resolution imaging is extremely difficult due to the inherent contradiction. Here two thermally activated delayed fluorescence (TADF)-actived coinage-metal clusters M S L (M=Ag or Cu) were synthesized by simple solvothermal reaction, where the cooperation of heavy atom-rich character and TADF mechanism supports strong X-ray absorption and rapid luminescent collection of excitons.

Nonlinear Optical Phosphide CuInSiP: The Inaugural Member of Diamond-Like Family I-III-IV-V Inspired by ZnGeP.

Noncentrosymmetric phosphides have garnered significant attention as promising systems of infrared (IR) nonlinear optical (NLO) materials. Herein, a new quaternary diamond-like phosphide family I-III-IV-V and its inaugural member, namely, CuInSiP (CISP), were successfully fabricated by isovalent and aliovalent substitution based on ZnGeP. First-principles calculations revealed that CISP has a large NLO coefficient ( = 110.

Photoinduced large magnetic change at room temperature and radical-quenched spin glass in a cyanide-bridged Mn-Fe compound.

By the coordination assembly of a redox photoactive functional motif and a cyanide-bridged moiety, a cyanide-bridged Mn-Fe compound with large photoinduced magnetic change at room-temperature due to photoinduced electron transfer was obtanied. This compound also shows unprecedented radical-quenched spin glass in molecule based magnets.

Significant increase of the photoresponse range and conductivity for a chalcogenide semiconductor by viologen coating through charge transfer.

Widening the photoresponse range while enhancing the electrical properties of semiconductors could reduce the complexity and cost of photodetectors or increase the power conversion efficiency of solar cells. Surface doping through charge transfer with organic species is one of the most effective and widely used approaches to achieve this aim. It usually features easier preparation over other doping methods but is still limited by the low physicochemical stability and high cost of the used organic species or low improvement of electrical properties.

Excellent Nonlinear Optical M[M Cl][Ga S ] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy.

The typical chalcopyrite AgGaQ (Q = S, Se) are commercial infrared (IR) second-order nonlinear optical (NLO) materials; however, they suffer from unexpected laser-induced damage thresholds (LIDTs) primairy due to their narrow band gaps. Herein, what sets this apart from previously reported chemical substitutions is the utilization of an unusual cationic substitution strategy, represented by [[SZn ]S + [S Zn ]S + 11ZnS ⇒ MS + [M Cl]S + 11GaS ], in which the covalent S Zn units in the diamond-like sphalerite ZnS are synergistically replaced by cationic M Cl units, resulting in two novel salt-inclusion sulfides, M[M Cl][Ga S ] (M = A/Ba, A = K, 1; Rb, 2). As expected, the introduction of mixed cations in the GaS anionic frameworks of 1 and 2 leads to wide band gaps (3.

Selectivity Control in the Direct CO Esterification over Pd@UiO-66: The Pd Location Matters.

The selectivity control of Pd nanoparticles (NPs) in the direct CO esterification with methyl nitrite toward dimethyl oxalate (DMO) or dimethyl carbonate (DMC) remains a grand challenge. Herein, Pd NPs are incorporated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X=-H, -NO , -NH ), affording Pd@UiO-66-X, which unexpectedly exhibit high selectivity (up to 99 %) to DMC and regulated activity in the direct CO esterification. In sharp contrast, the Pd NPs supported on the MOF, yielding Pd/UiO-66, displays high selectivity (89 %) to DMO as always reported with Pd NPs.

Bottom-Up Photosynthesis of an Air-Stable Radical Semiconductor Showing Photoconductivity to Full Solar Spectrum and X-Ray.

Single-component semiconductors with photoresponse to full solar spectrum are highly desirable to simplify the device structure of commercial photodetectors and to improve solar conversion or photocatalytic efficiency but remain scarce. This work reports bottom-up photosynthesis of an air-stable radical semiconductor using BiI and a photochromism-active benzidine derivative as a photosensitive functional motif. This semiconductor shows photoconductivity to full solar spectrum contributed by radical and non-radical forms of the benzidine derivative.

Cs Zn P S I : the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs.

Chalcohalides not only keep the balance between the nonlinear optical (NLO) coefficient and wide band gap, but also provide a promising solution to achieve sufficient birefringence for phase-matching ability in NLO crystals. In this study, a novel chalcohalide, Cs Zn P S I (1) is successfully synthesized, by incorporating the highly electropositive Cs and the large electronegative I element into the zinc thiophosphate. Its 3D open framework features an edge-shared by distorted [ZnS ], ethanol-like [P S ], and unusual [ZnS I ] polyhedrons, which is inconsistent with the soft-hard-acids-bases theory.

Breaking the bottleneck of simultaneously wide band gap and large nonlinear optical coefficient by a "pore reconstruction" strategy in a salt-inclusion chalcogenide.

The template-based design of the crystal structure is a direct and highly efficient method to achieve optimal nonlinear optical (NLO, meaning second-order NLO) performances. The structural flexibility of porous salt-inclusion chalcogenides (SICs) provides an alternative platform for modulating the enlargement of the band gap (that is generally positive with laser-induced damage threshold) and second harmonic generation (SHG) response simultaneously. By applying the "pore reconstruction" strategy to SIC [KCl][MnGaS] (1), a new derivative KRb[KCl][LiMnGaS] (2) is successfully isolated, which unusually features a heterologous nanopore framework with inner diameters of 8.

Improving X-ray Scintillating Merits of Zero-Dimensional Organic-Manganese(II) Halide Hybrids via Enhancing the Ligand Polarizability for High-Resolution Imaging.

Luminescent metal halides have been exploited as a new class of X-ray scintillators for security checks, nondestructive inspection, and medical imaging. However, the charge traps and hydrolysis vulnerability are always detrimental to the three-dimensional ionic structural scintillators. Here, the two zero-dimensional organic-manganese(II) halide coordination complexes and were synthesized for improvements in X-ray scintillation.

Highly Sensitive Direct X-Ray Detector Based on Copper(II) Coordination Polymer Single Crystal with Anisotropic Charge Transport.

Anisotropic charge transport plays a pivotal role in clarifying the conductivity mechanism in direct X-ray detection to improve the detection sensitivity. However, the anisotropic photoelectric effect of semiconductive single crystal responsive to X-ray is still lacking of theoretical and experimental proof. The semiconductive coordination polymers (CPs) with designable structures, adjustable functions, and high crystallinity provide a suitable platform for exploring the anisotropic conductive mechanism.

Nonlinear Optical Sulfides LiMGa S (M = Rb/Ba, Cs/Ba) Created by Li Driven 2D Centrosymmetric to 3D Noncentrosymmetric Transformation.

Cations that can regulate the configuration of anion group are greatly important but regularly unheeded. Herein, the structural transformation from 2D CS to 3D noncentrosymmetric (NCS, which is the prerequisite for second-order NLO effect) is rationally designed to newly afford two sulfides LiMGa S (M = Rb/Ba, 1; Cs/Ba, 2) by introducing the smallest alkali metal Li cation into the interlamination of 2D centrosymmetric (CS) RbGaS . The unusual frameworks of 1 and 2 are constructed from C -type [Ga S ] supertetrahedrons in a highly parallel arrangement.

Open honeycomb frameworks of sulphides AHgGaS (A = Rb, Cs) exhibiting infrared nonlinear optical properties.

A crystal structure with a diamond-like anionic framework belongs to a non-centrosymmetric macrostructure due to the aligned arrangement of tetrahedral units, meeting the premise of second-order nonlinear optical (NLO) materials. Herein, two new Hg-based sulphides, namely RbHgGaS (1) and CsHgGaS (2), which are isostructural and crystallise in the trigonal space group 3, are successfully isolated in sealed silica tubes by a solid-state reaction. The features of their three-dimensional open honeycomb frameworks are attributed to the parallel alignment of tetrahedral MS (M is disordered by 0.

[K PbX][Ga S ] (X = Cl, Br, I): The First Lead-Containing Cationic Moieties with Ultrahigh Second-Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV.

In contrast to anionic group theory of nonlinear optical (NLO) materials that second-harmonic generation (SHG) responses mainly originate from anionic groups, structural regulation on the cationic groups of salt-inclusion chalcogenides (SICs) is performed to make them also contribute to the NLO effects. Herein, the stereochemically active lone-electron-pair Pb cation is first introduced to the cationic groups of NLO SICs, and the resultant [K PbX][Ga S ] (X = Cl, Br, I) are isolated via solid-state method. The features of their three-dimensional structures comprise highly oriented [Ga S ] and [K PbX] frameworks derived from AgGaS , which display the largest phase-matching SHG intensities (2.

Material research from the viewpoint of functional motifs.

As early as 2001, the need for the 'functional motif theory' was pointed out, to assist the rational design of functional materials. The properties of materials are determined by their functional motifs and how they are arranged in the materials. Uncovering functional motifs and their arrangements is crucial in understanding the properties of materials and rationally designing new materials of desired properties.

AAgGaSe (A = Rb, Cs): second-harmonic generation responses realized through the parallel arrangement of AgSe and GaSe tetrahedrons.

Two new quaternary selenides AAgGaSe, (A = Rb, 1; Cs, 2) were synthesised solid-state reaction in sealed silica tubes. Compounds 1 and 2 crystallised in the monoclinic space group (no. 8) and their three-dimensional [AgGaSe] anionic frameworks were comprised of AgSe and GaSe tetrahedrons.