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Scintillators are essential in converting ionizing X‐rays and γ‐rays into visible light, with applications in medical diagnosis, security inspection, and non‐invasive detection. However, current scintillating materials exhibit unclear structure–function relationships. The performance of scintillators is intricately linked to their electronic band structure, particularly the intrinsic properties of excited states. Therefore, investigating the structural factors affecting scintillation performance is crucial for developing new scintillators. Therefore, Ba‐SMOF 1 ([Ba2(PyTS)(CH3OH)2(H2O)4]n) is synthesized using a pyrene‐based organic motif and metal Ba(II) ions, where PyTS4− refers to pyrene‐1,3,6,8‐tetrasulfonate. For the first time, the excited state of a pyrene‐based X‐ray scintillating metal–organic framework (MOF) is determined through comprehensive all‐electron excitation studies, including in situ experimental electron density and wave‐function analysis. The electron density maps exhibit a continuous overlap, attributed to the associative exciton behaviors among the closely packed PyTS4− linkers. These linkers are identified as the sources of both static and dynamic excimer emissions. The electron density studies reveal the role of excimers in pyrene‐based luminophores, highlighting that interchromophoric interactions are key to enhancing the performance of scintillating MOFs. This discovery opens new avenues for the practical application of scintillating MOFs. [ABSTRACT FROM AUTHOR]

Nonlinear optical (NLO) materials are of immense scientific and technological importance. However, debate has long prevailed theoretically regarding the structural origin of the second harmonic generation (SHG) effect. In this work, the experimental electron density (ED) of controversial β‐BaB2O4 (BBO) is studied by high‐resolution X‐ray diffraction, indicating that the [B3O6]3− motif dominates two large non‐zero SHG tensors (d222 and d311) while Ba atoms contribute mostly to the smallest one (d333), and the atomic SHG contributions of terminal O atoms in [B3O6]3− motifs are much larger than those of B and bridged O atoms, clarifying the disputes on its NLO response mechanism. Besides, the contraction of inner electron shells (5s25p6) of the Ba atom and partial covalent behavior of the Ba─O interaction are first observed experimentally. Furthermore, the SHG coefficients of BBO derived from experimental ED are in excellent agreement with those from bulk crystals, providing a high‐efficient and low‐cost method of screening high‐performance NLO materials with just an easy‐to‐obtain tiny crystal. [ABSTRACT FROM AUTHOR]

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 M6S6L6 (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. Excitingly, Ag6S6L6 (SC‐Ag) displays a high photoluminescence quantum yield of 91.6 % and scintillating light yield of 17420 photons MeV−1, as well as a low detection limit of 208.65 nGy s−1 that is 26 times lower than the medical standard (5.5 μGy s−1). More importantly, a high X‐ray imaging resolution of 16 lp/mm based on SC‐Ag screen is demonstrated. Besides, rigid core skeleton reinforced by metallophilicity endows clusters M6S6L6 strong resistance to humidity and radiation. This work provides a new view for the design of efficient scintillators and opens the research door for silver clusters in scintillation application. [ABSTRACT FROM AUTHOR]

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, ‐NO2, ‐NH2), 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. Both experimental and DFT calculation results prove that the Pd location relative to UiO‐66 gives rise to discriminated microenvironment of different amounts of interface between Zr‐oxo clusters and Pd NPs in Pd@UiO‐66 and Pd/UiO‐66, resulting in their distinctly different selectivity. This is an unprecedented finding on the production of DMC by Pd NPs, which was previously achieved by Pd(II) only, in the direct CO esterification. [ABSTRACT FROM AUTHOR]

Construction of heterojunctions to photocatalysts is one of the most promising approaches to improve charge separation efficiency; however, the established constructing processes usually require high‐temperature conditions and/or the adding of highly concentrated or expensive exotic species, and the improvement of effective contact and charge exchange between heterojunction components remains a problem. This work proposes an unprecedented "photobreeding" method and realizes the direct growth of Zn nanowires and Mott–Schottky heterojunctions from ZnS or viologen‐coated ZnS microspheres through a photochemical reaction at room temperature without external species, while demonstrating the hypothesis proposed 140 years ago on the formation of Zn in the photochromic process of ZnS. After photobreeding of the heterojunctions, the hydrogen production efficiency of the photocatalysts increases by 2 orders of magnitude. This inexpensive, facile and efficient synthetic method will find applications in H2 production, organic synthesis, CO2 reduction, nitrogen fixation, and so on. [ABSTRACT FROM AUTHOR]

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 BiI3 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. It has also the potential to detect X‐rays because of strong X‐ray absorption coefficient. This finding opens up a new synthetic method for radical semiconductors and may find applications on extending photoresponsive ranges of perovskites, transition metal sulfides, and other materials. [ABSTRACT FROM AUTHOR]

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 Pb2+ cation is first introduced to the cationic groups of NLO SICs, and the resultant [K2PbX][Ga7S12] (X = Cl, Br, I) are isolated via solid‐state method. The features of their three‐dimensional structures comprise highly oriented [Ga7S12]3− and [K2PbX]3+ frameworks derived from AgGaS2, which display the largest phase‐matching SHG intensities (2.5−2.7 × AgGaS2 @1800 nm) among all SICs. Concurrently, three compounds manifest band gap values of 2.54, 2.49, and 2.41 eV (exceeding the criterion of 2.33 eV), which can avoid two‐photon absorption under the fundamental laser of 1064 nm, along with the relatively low anisotropy of thermal expansion coefficients, leading to improved laser‐induced damage thresholds (LIDTs) values of 2.3, 3.8, and 4.0 times that of AgGaS2. In addition, the density of states and SHG coefficient calculations demonstrate that the Pb2+ cations narrow the band gaps and benefit SHG responses. [ABSTRACT FROM AUTHOR]

Introduction of photochromic properties into semiconductors confers semiconductors with smart behaviors, color‐related applications, and new modulation approaches. Photochromophores with electron‐transfer (redox) behavior, such as viologen and naphthalene diimide, are ideal functional motifs to design photochromic semiconductors owing to good adaptability to the solid matrix, but their reverse reactions are exclusively realized by the thermal mode, which is slow (in dozens of seconds or longer) and thus significantly hinders real applications in the fields that require high‐speed switching. This study reveals that photoexcitation in the electronic absorption band of the π‐aggregate of viologen cation radicals can successfully trigger reverse electron transfer quickly (in 1 s with a continuous‐wave 808 nm laser at a power density of 5 W cm−2; the photothermal effect is excluded), and the first single‐component all‐optically photochromic semiconductor is accordingly discovered. This discovery breaks through a traditional concept that reverse reactions of viologen compounds can not be triggered by the light, and provides a potential approach to realize all‐optical switch of single‐component photochromic smart semiconductors based on electron‐transfer photochromic functional motifs. [ABSTRACT FROM AUTHOR]

Similarities in sizes, shapes, and physical properties between carbon dioxide (CO2) and acetylene (C2H2) make it a great challenge to separate the major impurity CO2 from products in C2H2 production. The use of porous materials is an appealing path to replace current very costly and energy‐consuming technologies, such as solvent extraction and cryogenic distillation; however, high CO2/C2H2 uptake ratio with minor adsorption of C2H2 at standard pressure was only unexpectedly observed in scarce examples in recent years although the related research started early at 1950s, and general design strategies to realize this aim are still absent. This work has successfully developed an efficient PIET strategy and obtained the second highest CO2/C2H2 adsorption ratio for porous materials in a proof‐of‐concept MOF with a photochromism‐active bipyridinium zwitterion. An unprecedented photocontrollable gate effect, owing to change of interannular dihedral after photoinduced generation of radical species, was also observed for the first time. These findings will inspire design and synthesis of porous materials for high efficient gas adsorption and separation. [ABSTRACT FROM AUTHOR]

Exploring nonlinear optical (NLO) functional motifs (FM, the structural origin of NLO efficiency) is vital for the rational design of NLO materials. Normal spectrum techniques applied in studying photon exciting materials are invalid for NLO materials, in which electrons are not excited substantially but only distorted under laser. A general strategy of determining NLO FM is proposed by comparative studies of experimental electron density (ED) without and under the laser. The in situ experimental ED and wavefunction of typical NLO material LiB3O5 (LBO) under dark and 360 and 1064 nm lasers are investigated. Compared with the initial state under dark, the ED of [B3O5]− unit at functional states under laser irradiation exhibits remarkable changes of topological atomic and bond properties, confirming the NLO FM being [B3O5]−. The work extracts for the first time the FM of a NLO material experimentally and highlights the crucial role of in situ ED analysis in studying NLO mechanisms. [ABSTRACT FROM AUTHOR]

A large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt‐inclusion chalcogenide (SIC), Li[LiCs2Cl][Ga3S6] (1), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS4 tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS2), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap. [ABSTRACT FROM AUTHOR]

2,4,6‐Tri(4‐pyridyl)‐1,3,5‐triazine (tpt) is a widely used ligand for functional coordination compounds. In this work, tpt has shown unprecedented photochromism in the crystalline state. Experimental and theoretical data has revealed that the photocoloration of tpt very likely originates from intramolecular charge separation and the formation of a triplet diradical product. This finding demonstrates a new simple, neutral photochromic molecule and endows the tpt molecule and related compounds with potential optical applications. [ABSTRACT FROM AUTHOR]

Keywords: Heterogeneous Catalysis; Lewis Acid Sites; Metal–Organic Frameworks; Microenvironment Modulation; PalladiumHeterogeneous Catalysis. In their Research Article (e202311625), Weijie Yang, Hai‐Long Jiang et al. incorporate Pd nanoparticles into MOFs. The obtained catalyst exhibits high selectivity for dimethyl carbonate in the direct CO esterification with methyl nitrite...By Shuaishuai Hu; Chenfan Xie; Yu‐Ping Xu; Xuelu Chen; Ming‐Liang Gao; He Wang; Weijie Yang; Zhong‐Ning Xu; Guo‐Cong Guo and Hai‐Long JiangReported by Author; Author; Author; Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

Summary of main observation and conclusion: RuCl3 catalyst system has many advantages for the hydro‐esterification of methyl formate and ethylene to methyl propionate. However, the unsatisfied performance restricts the development of this route. In this work, high‐performance RuCl3 catalyst systems (RuCl3‐[PPN]Cl‐Et4NI and RuCl3‐NaI) are firstly reported for this reaction. In RuCl3‐[PPN]Cl‐Et4NI catalyst system, the conversion of methyl formate and the selectivity to methyl propionate are 93.9% and 90.9% at mild reaction conditions (165°C, 2.5 MPa), respectively. Noticeably, a simple inorganic RuCl3‐NaI catalyst system achieves 88.8% conversion of methyl formate and 97.6% selectivity to methyl propionate (86.7% yield) at same conditions. NaI, as a promoter, may inhibit the decomposition of methyl formate and be conducive to the formation of methyl propionate. The effects of solvents and promoters are investigated in detail. In addition, the reaction mechanism has been also analyzed. It is hoped to lay a certain foundation for further industrial application. [ABSTRACT FROM AUTHOR]

Breaking the intrinsic rule of semiconductors that conductivity increases with increase of temperature and realizing a dramatic dropping of conductivity at high temperature may arouse new intriguing applications, such as circuit overload or over‐temperature protecting. This goal has now been achieved through T‐type electron‐transfer photochromism of one organic semiconductor assembled by intermolecular cation⋅⋅⋅π interactions. Conductivity of the viologen‐based model semiconductor (H2bipy)(Hox)2 (H2bipy=4,4′‐bipyridin‐1,1′‐dium; ox=oxalate) increased by 2 orders of magnitude after photoinduced electron transfer (a record for photoswitchable organic semiconductors) and generation of radical cation⋅⋅⋅π interactions, and fell by approximately 81 % at 100 °C through reverse electron transfer and degeneration of the radical cation⋅⋅⋅π interactions. The model semiconductor has at least two different electron transfer pathways in the decoloration process. [ABSTRACT FROM AUTHOR]

A big challenge for nonlinear optical (NLO) materials is the application in high power lasers, which needs the simultaneous occurrence of large second harmonic generation (SHG) and high laser induced damage threshold (LIDT). Herein we report the preparation of a new Ga2Se3 phase, which shows the SHG intensities of around 2.3 times and the LIDT of around 16.7 times those of AgGaS2 (AGS), respectively. In addition, its IR transparent window ca. 0.59–25 μm is also significantly wider than that of AGS (ca. 0.48–≈11.4 μm). The occurrence of the strong SHG responses and good phase‐matching indicate that the structure of the new Ga2Se3 phase can only be non‐centrosymmetric and have a lower symmetry than the cubic γ‐phase. The observed excellent SHG and phase‐matching properties are consistent with our diffraction experiments and can be well explained by using the orthorhombic models obtained through our high throughput simulations. [ABSTRACT FROM AUTHOR]

Superlattice materials offer new opportunities to modify optical and electrical properties of recently emerging 2D materials. The insertion of tetraethylbenzidine (EtDAB) into interlamination of the established 2D PbI2 semiconductor through a mild solution method yielded the first lead iodide superlattice, EtDAB⋅4PbI2 (EtDAB=tetraethylbenzidine), with radical and non‐radical forms. The non‐radical form has a non‐ionic structure that differs from the common ionic structures for inorganic–organic hybrid lead halides. The radical form shows five orders of magnitude greater conductance and broader photoconductive response range (UV/Vis → UV/Vis‐IR), than pure PbI2 and the non‐radical form of the superlattice. Lead the way: The first lead‐iodide superlattice constructed from non‐ionic organic molecules and PbI2 through van der Waals interactions is a new type of inorganic–organic hybrid and has a radical and a non‐radical form. The radical form has an almost five orders of magnitude greater conductivity and broader band photoconductive response than that of the non‐radical form or pure PbI2. [ABSTRACT FROM AUTHOR]

Abstract: Recently, the emergence of photoactive metal–organic frameworks (MOFs) has given great prospects for their applications as photocatalytic materials in visible‐light‐driven hydrogen evolution. Herein, a highly photoactive visible‐light‐driven material for H2 evolution was prepared by introducing methylthio terephthalate into a MOF lattice via solvent‐assisted ligand‐exchange method. Accordingly, a first methylthio‐functionalized porous MOF decorated with Pt co‐catalyst for efficient photocatalytic H2 evolution was achieved, which exhibited a high quantum yield (8.90 %) at 420 nm by use sacrificial triethanolamine. This hybrid material exhibited perfect H2 production rate as high as 3814.0 μmol g−1 h−1, which even is one order of magnitude higher than that of the state‐of‐the‐art Pt/MOF photocatalyst derived from aminoterephthalate. [ABSTRACT FROM AUTHOR]

Abstract: Nonlinear optical (NLO) materials with strong second harmonic generation (SHG) responses are technologically and scientifically important for tunable lasers. This work puts forward a new strategy for designing promising infrared nonlinear optical (IR‐NLO) materials with strong SHG responses by strengthening both the static and induced contributions via the high orientation of NLO functional motifs. Two new polyselenides Rb2Ge4Se10 and Cs2Ge4Se10 are studied to verify the strategy, they have 2D infinite ∞ 2[Ge4Se10]2− layers comprising highly oriented distorted GeSe4 tetrahedra. Their large SHG signals (8.0 and 8.5 times that of commercial AgGaS2) can be ascribed to both the static contribution enhancement from the high orientation of the local dipole moment of GeSe4 tetrahedra and the induced contribution enhancement from terminal and SeSe bonded Se atoms. The results confirm the effectiveness of the proposed approaches, shedding light on the exploration of practical IR‐NLO materials with maximized performance. [ABSTRACT FROM AUTHOR]

Abstract: We evaluated the individual atom contributions to the second harmonic generation (SHG) coefficients of LiCs2PO4 (LCPO) by introducing the partial response functionals on the basis of first principles calculations. The SHG response of LCPO is dominated by the metal‐cation‐centered groups CsO6 and LiO4, not by the nonmetal‐cation‐centered groups PO4 expected from the existing models and theories. The SHG coefficients of LCPO are determined mainly by the occupied orbitals O 2p and Cs 5p as well as by the unoccupied orbitals Cs 5d and Li 2p. For the SHG response of a material, the polarizable atomic orbitals of the occupied and the unoccupied states are both important. [ABSTRACT FROM AUTHOR]

A dual temperature- and light-responsive C2H2/C2H4 separation switch in a diarylethene metal-organic framework (MOF) is presented. At 195 K and 100 kPa this MOF shows ultrahigh C2H2/C2H4 selectivity of 47.1, which is almost 21.4 times larger than the corresponding value of 2.2 at 293 K and 100 kPa, or 15.7 times larger than the value of 3.0 for the material under UV at 195 K and 100 kPa. The origin of this unique control in C2H2/C2H4 selectivity, as unveiled by density functional calculations, is due to a guest discriminatory gate-opening effect from the diarylethene unit. [ABSTRACT FROM AUTHOR]

N, N′-Disubstituted bipyridinium (viologen) and N-monosubstituted bipyridinium compounds are well known for their electron-transfer (ET) photochromic behavior. Their modification has exclusively focused on the N-substituents to date. For the first time, we have studied the photochromic behavior when one pyridyl ring of the bipyridinium is substituted with a multifunctional azole group, and have found that two new coordination compounds based on N-methyl-4-pyridinium tetrazolate (mptz) zwitterion, [Zn(mptz)2Br2] ( 1) and [Cd3(mptz)2Cl6] n⋅4 n H2O ( 2), exhibit typical ET photochromic behavior owing to photoinduced ET from halogen anion to the mptz ligand. This work demonstrates a new simple, neutral photoactive molecule with electron-accepting ability, which may act as a photoactive component for materials with potential photoswitching and photocatalysis applications. [ABSTRACT FROM AUTHOR]

Electron-transfer (redox) thermochromism was successfully used for switching the conductance of semiconductors, by introducing a thermally active organic component into an inorganic semiconducting framework. A moisture-resistant semiconductor {(MV)2[Pb7Br18]} n (MV2+=methyl viologen cation) has been prepared through an in situ synthetic method for MV2+. It features a rare 3D haloplumbate open framework and unprecedented electron-transfer thermochromic behavior in haloplumbates. The electrical conductivity of this compound dropped significantly after coloration and restored after decoloration, which was satisfactorily explained by valence band XPS and theoretical data. This work not only offers a new approach to modify electrical properties of semiconductors without altering components or structures, but may lead to the development of over-temperature color indicators, circuit overload protectors or photovoltaic materials. [ABSTRACT FROM AUTHOR]

The first indiumsilicate oxysulfide Ba2In2Si3O10S ( 1) was obtained by an alkali polychalcogenide flux method through a high-temperature solid-state reaction. It crystallizes in the non-centrosymmetric space group Pca21 (No. 29), with a = 23.060(6), b = 5.2954(6), c = 8.779(2) Å, and Z = 4. Its three-dimensional (3D) framework is constructed from one-dimensional (1D) infinite ∞1[In2O7S2/2] double octahedral chains bridged by corner-sharing Si tetrahedral trimers [Si3O10]8-, yielding a 3D framework with the channels filled with Ba2+ cations along the b direction. It is unprecedented in that the two distorted indium octahedra in 1 face-share to form a [In2O7S2] dimer in indium oxides and oxide chalcogenides. [ABSTRACT FROM AUTHOR]

Crystalline nanotube array would create great opportunity for novel electrical application. Herein we report the first example of a metal halide based crystalline nanotube array which is constructed from an unprecedented giant [PbII18I54(I2)9] wheel cluster, as determined by synchrotron Xray diffraction. The electrical properties of the single crystal were studied and the present compound shows typical semiconductivity and highly anisotropic conductivity. [ABSTRACT FROM AUTHOR]

A new layered compound, Hg5AsS2I3, has been synthesized in the quaternary system mercury/arsenic/chalcogen/halogen by a moderate-temperature solid-state reaction. The compound crystallizes in the space group C2/ c of the monoclinic system, and its structure consists of ∞1[Hg(1)2Hg(2)2As2/2S2] eight-membered-ring chains bridged by Hg atoms to form [Hg(1)2Hg(2)2Hg(3)As2/2S2] layers with inner- and interlayer electrostatic interactions between I and Hg. The optical properties were investigated by means of diffuse reflectance and FTIR spectra. The electronic band structures, along with density of states (DOS) calculations by DFT, indicate that the title compound is a semiconductor, and its optical absorption mainly leads to charge transitions from I-5p, As-4p and S-3p states to Hg-6s states, and both I(1) and I(2) atoms contribute to the top of the valence bands. [ABSTRACT FROM AUTHOR]

Two new metal pnictide halides, (Hg9.75As5.5)(GaCl4)3 and (Hg13Sb8)(ZnBr4)4, have been prepared by solid-state reactions. Their structures feature 3D cationic host frameworks built of mercury pnictide polyhedra and form 1D tunnels filled with discrete guest halide polyanions; the guests and hosts are assembled by van der Waals interactions. Both complexes exhibit good single-crystal humidity sensitivity, with a humidity sensitivity factor as big as three orders of magnitude, a quick resistance response, fast recovery, and good reproducibility. This study provide a new way to design promising resistive humidity detectors by introducing van der Waals host-guest interactions into their structures. [ABSTRACT FROM AUTHOR]

We demonstrate herein a promising pathway towards low-energy CO2 capture and release triggered by UV and visible light. A photosensitive diarylethene ligand was used to construct a photochromic diarylethene metal-organic framework (DMOF). A local photochromic reaction originating from the framework movement induced by the photoswitchable diarylethene unit resulted in record CO2-desorption capacity of 75 % under static irradiation and 76 % under dynamic irradiation. [ABSTRACT FROM AUTHOR]

Four new inorganic supramolecular complexes, [Hg4P2][ZrCl6] ( 1), [Hg4As2][ZrCl6] ( 2), [Hg4P2][HfCl6] ( 3), and [Hg4As2][HfCl6] ( 4), have been prepared by moderate-temperature solid-state reactions. All compounds crystallize in the space group Pbca of the orthorhombic system with Z = 8. Their structures are built up of mercury pnictide cationic hosts and distorted octahedral [MCl6]2- (M = Zr, Hf) guests. The isolated octahedral guests consist of tetravalent Zr4+ and Hf4+ cations coordinated by chlorine atoms and are embedded in the infinite channels formed by the host framework. Their optical properties were investigated in terms of their diffuse reflectance and FTIR spectra. The electronic band structures along with densities of states (DOS) calculated by DFT indicate that all of the title compounds are semiconductors with direct band gaps, and their optical absorptions mainly originate from charge transitions from Cl 3p and P 3p/As 4p states to Hg 6s, Hg 5p, and Zr 4d/Hf 5d states. Optical dielectric constant calculations show that 1- 4 possess dielectric anisotropy, which is consistent with their structural studies. [ABSTRACT FROM AUTHOR]

In a state of disorder: An inorganic supramolecular complex, (Hg6P4)(CuCl3)2, was prepared that undergoes a ferroelectric transition at about 37   K, and its spontaneous polarization was determined to be about 114   μC m−2 in the polycrystalline form using the high ‐ precision pyroelectric current method. Weak electrostatic supramolecular interactions in 1 lead to the dynamic disorder of ions and ferroelectric transition. [ABSTRACT FROM AUTHOR]

The first bulk electron-transfer photochromic compound with intrinsic second-order nonlinear optical (NLO) photoswitching properties has been synthesized. This system employs an electron-transfer photoactive asymmetric viologen ligand coordinated to a zinc(II) center. [ABSTRACT FROM AUTHOR]

Scintillators can convert the ionizing radiation into visible light and are crucial in X/γ‐ray detectors. Commercial detectors often use multiple scintillators with photodetector arrays, where optical crosstalk can degrade the performance. Chiral scintillators, emitting circularly polarized light, offer a promising solution for regulating the direction of light propagation to enhance X‐ray detecting merits. Here novel chiral metal‐organic polymers have been developed via photopolymerization, using chiral polymeric monomers and 0D Mn(II)‐based organic‐metal halide hybrid scintillators, achieving luminescence dissymmetry factors (glum) of 5.823 × 10−2 and −2.877 × 10−2. Two such scintillators, (atpp)2MnCl4·0.5H2O (MnCl4−1) and (atpp)2MnBr4 (MnBr4−2), exhibit excellent X‐ray scintillation rooted in tetrahedral [MnX4]2− crystal field. Compound MnBr4−2, with heavier bromine atoms, shows superior performance with a detection limit of 0.117 µGyair s−1, compared to 0.330 µGyair s−1 of MnCl4−1, both surpassing the medical diagnostic standard of 5.50 µGyair s−1. The chiral metal‐organic polymer film derived from MnBr4−2 has achieved a resolution up to 14.84 lp mm−1, exceeding medical standards for dental (2.0 lp mm−1) and breast cancer (10.0 lp mm−1) imaging. These advancements in chiral scintillators hold significant promise for high‐resolution X‐ray medical imaging applications. [ABSTRACT FROM AUTHOR]