Achieving Intrinsic Dual-Band Excitonic Luminescence from a Single Three-Dimensional Perovskite Nanoparticle Through Ni^(2+)-Mediated Halide Anion Exchange

Rapid halide anion exchange easily occurring in metal-halide perovskite nanoparticles(NPs)makes it nearly impossible to create a single three-dimensional(3D)CsPbX_(3)(X=Cl,Br,I)NP that simultaneously comprises two separate perovskite components.To circumvent this problem,we first propose a Ni^(2+)-mediated halide anion-exchange strategy in zero-dimensional(0D)Ni^(2+)-doped Cs_(4)PbBr_(6)(Cs_(4)PbBr_(6):Ni)perovskites to achieve ultra-stable 3D CsPbX_(3)NPs with two coexisting different perovskite individuals of CsPbCl_(3)and/or CsPbBr_(3).By combining the experimental results with first-principles calculations,we confirm that the completely isolated[PbBr_(6)]4−octahedra in 0D Cs_(4)PbBr_(6):Ni NPs can restrict rapid halide anion exchange and the anion diffusion preferentially proceeds in the proximity of substitutional NiPb centers,namely[NiBr_(6)]4−octahedra in a meta-stable state,rather than in the 0D Cs_(4)PbBr_(6)and residual 3D CsPbBr_(3)regions,thereby delivering intrinsic dual-band excitonic luminescence from a single 3D CsPbX_(3)NP with a more stable and efficient CsPbCl_(3)component as compared to its counterparts synthesized using conventional methods.These new insights regarding the precise control of halide anion exchange enable the preparation of a new type of high-efficiency perovskite materials with suppressed anion interdiffusion for prospective optoelectronic devices.

Ultrasensitive polarized-light photodetectors based on 2D hybrid perovskite ferroelectric crystals with a low detection limit

Polarized-light photodetectors are the indispensable elements for practical optical and optoelectronic device applications.Two-dimensional(2D)hybrid perovskite ferroelectrics,in which the coupling of spontaneous polarization(P_(s))and light favors the dissociation of photo-induced carriers,have taken a booming position within this portfolio.However,polarized-light photodetectors with a low detectionlimit remain unexplored in this 2D ferroelectric family.In this work,the high-quality individual crystals of a 2D perovskite ferroelectric,BA_(2)CsPb_(2)Br_(7)(1,where BA^(+)is n-butylammonium),were used to fabricate ultrasensitive polarized-light detectors.Its unique bilayered structural motif results in quite strong electric and optical anisotropy with a large absorption ratio of a_(c)/α_(a)≈3.2(λ=405 nm).Besides,the presence of ferroelectric Psalso endows high built-in electric field along the polar c-axis that favors photoelectric activities.Under an extremely low detectable limit of 40 n W/cm^(2),the detector of 1 exhibits a notable dichroism ratio(I_(ph)^(c)/I_(ph)^(a)≈1.5),a large responsivity of~39.5 m A/W and a specific detectivity of~1.2×10^(12)Jones.Moreover,crystal-based devices of 1 also exhibit a fast response speed(~300μs)and excellent anti-fatigue merits.This work highlights great potentials of hybrid perovskite ferroelectrics toward polarized-light photodetection.

Achieving effective balance between bandgap and birefringence by confining p-conjugation in an optically anisotropic crystal

Birefringence arises when the propagation speed and refractive index of light in an optically anisotropic crystal changes in response to the direction of vibration.Thus,birefringence belongs to linear optical anisotropy and is a key parameter for linear optoelectronic functional crystals,such as birefringent crystals,which are widely used to modulate the polarization of light in optoelectronic areas[1].In terms of practical applications,there is still an urgent need for wide-bandgap birefringent crystals as they allow for the modulation of light polarization in short-wavelength UV waves and even in the deep-UV spectral region.

Stabilizing the Extrinsic Porosity in Metal-Organic Cages-Based Supramolecular Framework by In Situ Catalytic Polymerization

Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of guest molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.

3D metal-organic frameworks based on lanthanide-seamed dimeric pyrogallol[4]arene nanocapsules

Two novel 3D metal-organic frameworks(MOFs)with cds network,{[Me NH_3]_7[Ln_8(Pg C_2)_2(H_2O)_y(HCOO)_7]}_n·x(Solvent)(FJI-Y4,FJI=Fujian Institute,Ln=Gd,y=12;FJI-Y5,Ln=Dy,y=11;Pg C_2=C-ethylpyrogallol[4]arene),based on unprecedented dimeric pyrogallol[4]arene-based Ln_8metal-organic nanocapsule(MONC)supramolecular building blocks and formate linkers,have been prepared under solvothermal conditions.To our best of knowledge,they present not only the first two examples of 3D hierarchical structures constructed from MONCs in metal-pyrogallol[4]arene system,but also the first two examples of MOFs based on lanthanide MONCs.Remarkably,the inner cavity volume of the Ln_8capsule in FJI-Y4 and FJI-Y5 is approximately151?~3,which is larger than those found in previous transition metal-seamed dimeric Pg C_n-based MONCs.Magnetic investigation on FJI-Y4 suggests a significant magnetocaloric effect(23.97 J kg^(-1)K^(-1),ΔH=7 T,2.5 K),while FJI-Y5 exhibits slow relaxation of the magnetization.

A Nonlinear Optical Switchable Sulfate of Ultrawide Bandgap

Nonlinear optical(NLO)switchable materials have attracted intense attention because of their promising applications in optoelectronic devices.However,previous studies are mainly limited to molecular-based compounds that usually exhibit narrow bandgaps.Here,we report all-inorganic Li_(9)Na_(3)Rb_(2)(SO_(4))_(7) as an ultrawide-bandgap NLO switchable material.

Nonpolar Na_(10)Cd(NO_(3))_(4)(SO_(3)S)_(4) Exhibits a Large Second-Harmonic Generation

Conventional wisdom says that nonpolar structures do not favorably produce strong second-harmonic generation(SHG)responses since the polarization in their microscopic functional groups are counteracted.Herein,we report the first nonlinear optical thiosulfate,Na_(10)Cd(NO_(3))_(4)(SO_(3)S)_(4),which crystallizes in a nonpolar space group of P−4.However,this thiosulfate exhibits a strong SHG response of about 4.2 times that of the benchmark KH2PO4,which is larger than those of polar sulfates.According to first-principles calculations and a flexible dipole model,the SHG enhancement is mainly ascribed to the larger flexibility of the S=S bond in the SO_(3)S tetrahedra in comparison with the S–O bond in the SO4 tetrahedra.These findings indicate that constructing flexible bonds is an effective strategy to design highperformance nonlinear optical materials regardless of polarity.

Boosting self-trapped exciton emission from Cs_(3)Cu_(2)I_(5)nanocrystals by doping-enhanced exciton-phonon coupling

Self-trapped excitons(STEs)emission from halide perovskites with strong exciton-phonon coupling has attracted considerable attention due to the widespread application in optoelectronic devices.Nevertheless,the in-depth understanding of the relationship between exciton-phonon coupling and luminescence intensity remains incomplete.Herein,a doping-enhanced exciton-phonon coupling effect is observed in Cs_(3)Cu_(2)I_(5)nanocrystals(NCs),which leads to a remarkable increasement of their STEs emission efficiency.Mechanism study shows that the hetero-valent substitution of Cu+with alkaline-earth metal ions(AE^(2+))causes a greater degree of Jahn-Teller distortion between the ground state and excited state structures of[Cu_(2)I_(5)]_(3)-clusters as evidenced by our spectral analysis and first-principles calculations.As a consequence,an X-ray detector based on these Cs_(3)Cu_(2)I_(5):AE NCs delivers an X-ray imaging resolution of up to 10 lp·mm^(-1) and a low detection limit of 0.37μGyair·s^(-1),disclosing the potential of doping-enhanced exciton-phonon coupling effect in improving STEs-emission and practical application for X-ray imaging.

An ultra-stable microporous supramolecular framework with highly selective adsorption and separation of water over ethanol

A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that an ultra-pure ethanol(99.9%)can be obtained from the mixture of ethanol/water(95:5).Additionally,after refluxing the desolvated sample in 95%ethanol at 60℃for 5 h,the purity of ethanol rises up to 97.43%,which is obviously higher than 96.56%for 4 A molecular sieves.

Organic polystyrene and inorganic silica double shell protected lead halide perovskite nanocrystals with high emission efficiency and superior stability

The practical application of all-inorganic semiconductor lead halide perovskite nanocrystals(LHP NCs)has been limited by their poor stability.Recently,a lot of research on core-shell structure has been done to improve the stability of perovskite NCs,but the effect was far from the application requirements.Herein,we,for the first time,report a convenient approach to synthesize organic-inorganic double shell CsPbBr_(3)@SiO_(2)@polystyrene(PS)NCs with an inter-core of CsPbBr_(3),the intermediate layer of SiO_(2)shell,and outmost PS shell.Particularly,the CsPbBr_(3)@SiO_(2)@PS NCs maintained more than 90%of their initial photoluminescence(PL)intensity under one month's ultraviolet lamp irradiation or in 85℃ and 85%relative humidity(RH)condition.The white-light-emitting-diodes(WLEDs)were fabricated by encapsulating commercial InGaN chip with CsPbBr_(3)@SiO_(2)@PS NCs and K2SiF6:Mn^(4+)(KSF:Mn^(4+))phosphor with a luminous efficacy of~100 lm/W at 20 mA current and a color gamut of 128%of the National Television Standards Committee(NTSC)standard.In addition,these WLEDs still maintain 91%of the initial luminous efficacy after 1200 h of continuous lighting.These results demonstrated that double shell-protected CsPbBr_(3)perovskite NCs have great potential in the field of WLEDs.

An Ultrastable π-π Stacked Porous Organic Molecular Framework as a Crystalline Sponge for Rapid Molecular Structure Determination

The crystalline sponge method is a pragmatic and promising strategy for molecular structure determination.However,the dominant metal-organic framework crystal sponge platforms always face poor chemical stability,especially solvent instability,hampering their application in a vaster domain.Herein,we report an ultrastable π-π stacked porous organic molecular framework which exhibits permanent porosity,high thermal stability,and good chemical resistance.It can efficiently implement an approach to molecular structure determination via a single-crystal-to-single-crystal transformation.This is the first example utilizing π-π stacked porous organic molecular framework as“crystalline sponge”to determine a wide variety of guests,ranging from hydrophilic to hydrophobic,and from aliphatic to aromatic,which complements the crystalline sponges based on the famous metal-organic frameworks.More importantly,it can achieve rapid structure determination of small molecules within 3 h.

Tuning the Structure of Fe-Tetracarboxylate Frameworks Through Linker-Symmetry Reduction

The design and synthesis of stable metal–organic frameworks(MOFs)have been a core obstacle in the widespread application of these functional crystalline porous materials,because of the stability limitations of MOFs under harsh operating conditions.Herein,a highly stable microporous MOF based on the Fe_(3)O cluster(PCN-678)has been synthesized using a tetracarboxylate ligand.Utilizing symmetry reduced tetratopic carboxylate ligand,a mesoporous MOF(PCN-668)could be obtained in which nanoscale cage-like building units and one-dimensional(1D)channels coexist.The neighboring cages were mutual diastereomers in PCN-668 due to the further reduction of the Cs symmetry of the free ligand to C1 symmetry after self-assembly.Furthermore,the acid stability of this mesoporous MOF was improved via postsynthetic metal exchange to chromium(PCN-668-Cr).The PCN-668-Cr exhibited very high stability in both acidic and basic aqueous solutions(pH=1–11).Additionally,the mesoporous MOF showed a high total gravimetric methane uptake(∼500 cm^(3) g^(−1) at 100 bar),while the microporous MOF showed a high volumetric methane storage capacity of 147 cm3 cm−3 at room temperature.

Research Article Acetic acid-mediated rapid cubic-to-hexagonal(α-β)phase transformation for ultra-bright lanthanide-dopedβ-NaYF_(4)nanobioprobes

Hexagonal-phase NaYF_(4)(β-NaYF_(4))has been acknowledged to be one of the most efficient doping hosts to prepare bright lanthanide-doped luminescent nano-bioprobes for various biomedical applications.However,to date,it remains a great challenge to synthesize ultra-bright lanthanide-dopedβ-NaYF_(4)nano-bioprobes under a low reaction temperature by using conventional synthetic methods.Herein,we first develop an acetic acid(HAc)-mediated coprecipitation method for the preparation of ultrabright lanthanide-dopedβ-NaYF_(4)nanoprobes under a low reaction temperature at 200℃.Based on a series of comparative spectroscopic investigations,we show that the use of HAc in the reaction environment can not only promote the rapidα-βphase transformation of NaYF_(4)host at 200℃ within 1 h but also boost the absolute photoluminescence quantum yield(PLQY)of NaYF_(4)nanocrystals to 30.68%for near-infrared emission and to 3.79%for upconversion luminescence,both of which are amongst the highest values for diverse lanthanide-doped luminescent nanocrystals ever reported.By virtue of their superior nearinfrared luminescence,we achieve optical-guided dynamic vasculature imaging in vivo of the whole body at a high spatial resolution(23.8μm)under 980 nm excitation,indicating its potential for the diagnosis and treatment evaluation of vasculaturerelated diseases.

Fabricating ultralow-power-excitable lanthanide-doped inorganic nanoparticles with anomalous thermo-enhanced photoluminescence behavior

Trivalent lanthanide(Ln^(3+))-doped luminescent nanoparticles(NPs)have been extensively investigated as deep-tissue-penetration visual bioimaging agents owing to their exceptional upconversion and near-infrared(NIR)luminescence upon irradiation of NIR light.However,in most cases,the power density of irradiation used for in vivo biological imaging is much higher than that of the reported maximum permissible exposure(MPE)value of NIR light,which inevitably does great damage to the living organisms under study and thus impedes the plausible clinical applications.Herein,by using a facile syringe pump-aided shell epitaxial growth method,we construct for the first time a new class of Ln^(3+)-doped KMgF_(3):Yb/Er@KMgF_(3)core-shell NPs that can be activated by utilizing a 980-nm xenon lamp or diode laser with an ultralow excitation power density down to 0.08 mW cm^(−2),a value that is approximately 4 orders of magnitude lower than the MPE value set by the American National Standards Institute(ANSI)for safe bioimaging in vivo.By combining the comparative spectroscopic investigations with atomic-resolved spherical aberration corrected transmission electron microscopy(AC-TEM)characterization,we find that the reduced crystallographic defects are the primary cause underlying such an ultralow-power-excitable feature of the KMgF_(3):Yb/Er@KMgF_(3)core-shell NPs.And,by the same token,the resultant KMgF_(3):Yb/Er@KMgF_(3)core-shell NPs also exhibit an anomalous thermo-enhanced photoluminescence(PL)behavior coupled with an excellent photothermal stability that cannot occur in other Ln^(3+)-doped core-shell NPs.These findings described here unambiguously pave a new way to prepare high-quality Ln^(3+)-doped luminescent NPs with desirable ultralow-power-excitable capability and photothermal stability for future biomedical applications.

Designing a deep-UV nonlinear optical monofluorophosphate

As structural variants of famous hexagonal tungsten bronzes,hexagonal tungsten oxides(HTO)represent an important family with fascinating functional properties,such as piezoelectric,ferroelectric,pyroelectric,and nonlinear optical(NLO)properties.However,none of them are transparent in the deep-UV spectral region,which limits their applications.Herein,we report the first HTO-type monofluorophosphate K_(3)Sc_(3)(PO_(4))(PO_(3)F)_(2)F_(5)(I)with deep-UV transparency.Such a monofluorophosphate is NLO-active with a phase-matchable powder second harmonic generation efficiency of 0.9 times that of KH_(2)PO_(4)at 1,064 nm.Importantly,the UV-Vis reflectance spectrum indicates that it is deep-UV transparent down to 200 nm.This work pushes the transparent window of NLO materials with HTO-type structures down to the deep-UV spectral region for the first time and opens up a new door for HTO materials.

A Novel Self-Penetrated Framework with New Topology Based on Rigid Ligands

A novel coordination polymer,formulated as Zn_(6)(TIB)_(4)(BPTC)_(3)(DMA)_(4)(H_(2)O)_(10)[TIB=1,3,5-tris(1-imidazolyl)-benzene,H_(4)BPTC=3,3',5,5'-biphenyltetracarboxylate],has been synthesized and structurally characterized.Further investigations reveal that it presents a new topology(topological symbol{6^(2).8^(4)}{6^(3)}4{6^(5).8}6{6^(6)}2)based on self-penetration,and shows interesting fluorescent properties.

Maximizing the linear and nonlinear optical responses of alkaline tricyanomelaminate

High-performance bi-functional materials are in urgent demand for the next-generation integrated optical devices.In this work,we successfully synthesized the first tricyanomelaminate with bi-functional optical responses,namely Cs_(3)C_(6)N_(9)•H_(2)O(I),from its analogue Na_(3)C_(6)N_(9)•3H_(2)O by a facile ion exchange method.In contrast to Na_(3)C_(6)N_(9)•3H_(2)O,I realizes an optimal arrangement of𝜋π-conjugated(C_(6)N_(9))3−anion groups in its crystal structure.As a result,the second-order nonlinear optical(NLO)response is greatly enhanced from nearly zero of Na_(3)C_(6)N_(9)•3H_(2)O to∼9.8×KH_(2)PO_(4)of I.Furthermore,I exhibits a giant linear optical anisotropic response(i.e.birefringence)of 0.52 at the wavelength of 550 nm.Both responses are almost the largest among the inorganic compounds ofπ-conjugated rings,which indicates that I has great potential as a bi-functional optical crystal.Structural and theoretical analyses reveal the microscopic origin of excellent optical properties.This work would attract a lot of interest to the persistently neglected potential of tricyanomelaminates as linear optical and NLO crystals.

Successive magnetic ordering in two Co^(Ⅱ)-ladder metal-organic frameworks

Metal-organic frameworks showing successive magnetic ordering are far less common than inorganic compounds.Here,we report two metal-organic frameworks[Co^Ⅱ(ox)(bphy)·0.1(DMF)·0.1(Me OH)]n(1)and[Co3^Ⅱ(ox)3(bphy)2(DMF)2]n(2)comprised of zigzag and necklace Co^Ⅱ-ladders,respectively.Together with a previously reported compound[Co^Ⅱ(ox)(bphy)·0.2(DMF)]n(3)consisting of spiraling zigzag Co^Ⅱ-ladders,these three compounds provide a good system for comparative structural and magnetic studies.Comprehensive magnetic analysis reveals that the three compounds undergo long-range magnetic ordering at^2.6 K but exhibit vastly different short-range magnetic correlations:compound 1 shows short-range spin-canted antiferromagnetism ordering at^14.0 K;compound 2 demonstrates successive short-range antiferromagnetism ordering at^15.5and^12.6 K;compound 3 shows slow magnetic relaxation with Tb≈4.6 K.These results demonstrate long-range magnetic ordering is readily accessible in the frameworks of ox^2-bridging Co^Ⅱ-ladders linked by bphy,where short-range magnetic correlations can be systematicly tuned by the Co^Ⅱ-ladder structures.

Highly Efficient White-Light Emission Induced by Carboxylic Acid Dimers in a Layered Hybrid Perovskite

Broadband white-light emission in metal halides has been intensely explored because of their facile solution processability,structural adjustability,and high color rendering index.However,the most reported quantum yields for white-light emission remain low despite great efforts.Herein,we report a metal-halide layered perovskite,(HOOC_(4)H_(9)NH_(3))_(2)PbBr_(4),showing the typical white-light emission with a highly enhan ced quantumyield up to 21.2% compared to previously reported noncarboxyl layered hybrid perovskites(0.5-9%).Notably,mechanistic studies reveal that the distinctive carboxylic acid dimers largely increase the structure rigidity and in consequence reduce the nonradiative recombination induced by stretching vibration.To the best of our knowledge,this strategy is important in hybrid perovskites,which is effective and propagable to acquire prominent photoluminescence.This work will shed light on the design of highly emissive white-light materials involving intense intermolecular interaction and promote their potential in displaying application.

Activating Surface Dark Emitters in Lanthanide-Doped Ultrasmall Nanoparticles for Biological Applications Based on Interparticle Energy Transfer

Lanthanide-doped ultrasmall nanoparticles(NPs)are attractive for diverse applications because of their unique optical properties compared with their bulk materials;their practical use,however,is greatly limited by extremely weak photoluminescence(PL)associated with severe surface quenching.Herein,we demonstrate an effective strategy to activate surface dark emitters of Eu3+in ultrasmall Sc_(2)O_(3).