Polymeric cerium nitrate complex with 1,4 bis(phenylsulfinyl)butane (bphsb) [Ce(bphsb) 2(NO 3) 3] n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb ...Polymeric cerium nitrate complex with 1,4 bis(phenylsulfinyl)butane (bphsb) [Ce(bphsb) 2(NO 3) 3] n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb and cerium(Ⅲ) ion form a polymeric double bridge chain complex involving 18 membered macrometallocycles. Each cerium ion is coordinated by ten O atoms in a distorted 4,4 bicapped square antiprism. In the complex the disulfoxide ligand acts as bis monodentate O ligand bridging metal centers.展开更多
Lead-halide perovskites exhibit outstanding performance in X-ray detection due to their intrinsic features such as high charge carrier mobility,large atomic number,and long carrier lifetime,but the toxicity of lead is...Lead-halide perovskites exhibit outstanding performance in X-ray detection due to their intrinsic features such as high charge carrier mobility,large atomic number,and long carrier lifetime,but the toxicity of lead is regarded as the major factor hindering their development.Here,we introduce organic molecule(R)-(-)-2-methylpiperazine(R-MPz)into the bismuth-based structure to synthesize lead-free(R)-(H_(2)MPz)BiI_(5)(R-MBI).The high-quality centimeter-sized single crystals have been obtained,which show a low dark current and superior environmental stability.Particularly,the single-crystal device of R-MBI exhibits a highμτproduct up to 1.88×10^(-4)cm^(2)/V and a low trap density of 1.21×10^(10)cm^(-3).Further,the detector displays excellent detection sensitivity of 263.58μC Gy_(air)^(-1)cm^(-2)and a favorable low detection limit of 4.35μGyair/s,both of which meet the requirement for medical diagnostics.These findings shed light on the exploration of innovative bismuth-based hybrid perovskites for high-performance X-ray detection.展开更多
Polar semiconductors,particularly the emerging polar two-dimensional(2D)halide perovskites,have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarizationgenerated photoelec...Polar semiconductors,particularly the emerging polar two-dimensional(2D)halide perovskites,have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarizationgenerated photoelectric effects.However,the constraints on the organic cation's choice are still subject to limitations of polar 2D halide perovskites due to the size of the inorganic pocket between adjacent corner-sharing octahedra.Herein,a mixed spacer cation ordering strategy is employed to assemble a polar 2D halide perovskite NMAMAPb Br_(4)(NMPB,NMA is N-methylbenzene ammonium,MA is methylammonium)with alternating cation in the interlayer space.Driven by the incorporation of a second MA cation,the perovskite layer transformed from a 2D Pb_(7)Br_(24)anionic network with corner-and face-sharing octahedra to a flat 2D PbBr_(4)perovskite networks only with corner-sharing octahedra.In the crystal structure of NMPB,the asymmetric hydrogen-bonding interactions between ordered mixed-spacer cations and 2D perovskite layers give rise to a second harmonic generation response and a large polarization of 1.3μC/cm^(2).More intriguingly,the ordered 2D perovskite networks endow NMPB with excellent self-powered polarization-sensitive detection performance,showing a considerable polarization-related dichroism ratio up to 1.87.The reconstruction of an inorganic framework within a crystal through mixed cation ordering offers a new synthetic tool for templating perovskite lattices with controlled properties,overcoming limitations of conventional cation choice.展开更多
Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an imp...Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.展开更多
The luminescent properties of two Eu3＋ compounds based on quinoline-2-car- boxylic acid （Hqc）, [Na2Eu2（qc）6（CH3COO）2（H2O）4].2DMF （1） and [Eu2（qc）6（H2O）6].3H2O （2）, as well as their syntheses and struc...The luminescent properties of two Eu3＋ compounds based on quinoline-2-car- boxylic acid （Hqc）, [Na2Eu2（qc）6（CH3COO）2（H2O）4].2DMF （1） and [Eu2（qc）6（H2O）6].3H2O （2）, as well as their syntheses and structures are reported. Both compounds are formed by slow evaporation at room temperature and exhibit zero dimensional dinuclear structures. It is worth mentioning that a 4.5-fold enhancement in luminescent quantum yield is achieved by reducing the nonradiative deactivation, through which the quantum yield increases remarkably to 67.62% for 1 compared with 12.18% for 2.展开更多
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 u...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.展开更多
Each of the four vertices in chiral tetrahedral hetero-nuclear metal carbonyl clusters SFeCoM（CO）<sub>8</sub>Cp′（Ⅲ-V） is chemically different and no symmetric element could be derived from prochiral ...Each of the four vertices in chiral tetrahedral hetero-nuclear metal carbonyl clusters SFeCoM（CO）<sub>8</sub>Cp′（Ⅲ-V） is chemically different and no symmetric element could be derived from prochiral cluster SFeCo<sub>2</sub>（CO）<sub>9</sub>（Ⅰ）. Its single optically active cluster obtained by suitable method could be served as a model catalyst for asymmetric catalysis.展开更多
A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group...A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group C2/c with a = 2.0448(3) nm, b= 1.5086(2) nm, c= 1.7923(2) nm, β=109.32(1)°. The structure of the title compound was solved by using 1 500 (I>3σ(I)) unique reflections and refined to R = 0.068. The structural features indicate the formal oxidation state of V(IV) + Ag (I), and partial charge transfer from Ag(I) to V(IV). The actions of reactants used in the reaction are discussed and a supposed formation process of the V2Ag2S4 cluster is suggested.展开更多
Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic framewor...Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic frameworks(HOFs),NKM-HOF-6 and NKM-HOF-7,featuring permanent microporosity.Upon treatment with hot acetone,NKM-HOF-6 undergoes a structural transformation into NKM-HOF-7,characterized by a transition from a 3D polycatenated framework to a 2D parallel displacement-stacked structure.This transformation leads to a reduction in the maximum pore size of NKM-HOF-7 and a decrease in the density of-CF_(3)groups within its channels,thereby enhancing its preferential affinity for C_(2)H_(6)over C_(2)H_(4).The adsorption capacity difference between C_(2)H_(6)and C_(2)H_(4)in NKM-HOF-7 is 11.1 cm^(3)·g^(-1),with an IAST selectivity of 1.77,surpassing the corresponding values for NKM-HOF-6(9.6 cm^(3)·g^(-1)and 1.56,respectively).Breakthrough experiments further reveal that NKM-HOF-7 achieves nearly twice the separation efficiency of NKM-HOF-6 for C_(2)H_(6)/C_(2)H_(4)(10/90,V/V)mixtures.Theoretical calculations attribute this enhanced C_(2)H_(6)affinity to the synergistic effects of optimized pore dimensions and functionalized pore surfaces in NKM-HOF-7.These findings provide critical insights for the rational design of highly efficient C_(2)H_(6)-selective adsorbents.展开更多
Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic build...Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks(MOFs)and covalent organic frameworks(COFs),re sulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice.The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D_(2)/H_(2)separation(~3Å).Here,we successfully modulate the poro sity of supramolecular frameworks of[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters(L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO_(4)-or Cl^(-))by controlling the duration of self-assembly processes.By simply adjusting the reaction time,we obtain three[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)supramolecular frameworks:[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)(μ^(3)-OH)_(24)(ClO_(4))L_(12))]·(Cl)_(4)·(HCO_(2))_(7)(1),[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(ClO_(4))4·(Cl)_(6)·(HCO_(2))·(H_(2)O)10(2),and[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(Cl)_(11)·(H_(2)O)12(3).The different stacking patterns of the[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters in these frameworks lead to significantly varied stabilities and porosities.Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions.In contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon desolvation.The pores of compound 1 show higher affinity to D_(2)than H_(2),and the pore aperture diameter of compound 1(~3.06Å)meets the optimal porosity for D_(2)/H_(2)separation.Consequently,compound 1 demonstrates moderate D_(2)/H_(2)separation at 77 K(retention time:~7 min/g for D_(2)/H_(2)/Ne(10/10/80 vol%)in a flow of 5 mL/min).These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.展开更多
Peroxynitrite(ONOO^(-))is a highly reactive nitrogen species that plays pivotal roles in cell signal transduction and physiological or pathological progresses.However,commonly used ONOO^(-)optical imaging probes are s...Peroxynitrite(ONOO^(-))is a highly reactive nitrogen species that plays pivotal roles in cell signal transduction and physiological or pathological progresses.However,commonly used ONOO^(-)optical imaging probes are still hampered by high background/autofluorescence(fluorescence probe),short emission wavelength,or poor selectivity in the case of chemiluminescence.Herein,we report a facile method to prepare an activatable chemiluminescence probe(PPA-PEG)with good biocompatibility and functionality for in vivo autofluorescence-free imaging of ONOO^(-).The PPA-PEG consists of pyropheophorbide-a(PPA),a typical deep red photosensitizer that acts as both the recognition and signaling element,and 4-arm poly(ethylene glycol)(4-arm PEG),which improves the biosafety and water solubility of probe.These components can self-assemble into nanoparticles(namely PPA-PEG nanoprobe)in aqueous solution.The PPA-PEG nanoprobe showed an ultra-low chemiluminescence signal before interacting with ONOO^(-),but exhibited good selectivity,high sensitivity and a fast response toward ONOO^(-).The PPAPEG was successfully applied to image cellular ONOO^(-)changes,as well as the endogenous ONOO^(-)changes in inflammation models and subcutaneous or orthotopic hepatocellular carcinoma(HCC)tumors models in living mice.In vitro and in vivo studies verified the good detection and imaging capabilities of PPA-PEG for peroxynitrite,demonstrating suitable tissue penetration and a high signal-to-background ratio(SBR).Thus,our nanoprobe can serve as a valuable activatable chemiluminescence imaging tool for studying important peroxynitrite-related chemical and biological applications.展开更多
The transition metal catalyzed C-H bond functionalization of hydrocarbons has aroused great interests in recent years due to the potential opportunity of developing novel methodologies in synthesis and chemical proces...The transition metal catalyzed C-H bond functionalization of hydrocarbons has aroused great interests in recent years due to the potential opportunity of developing novel methodologies in synthesis and chemical processes.展开更多
Various ions and antibiotics,widely used in industry and clinical medicine,respectively,are massively discharged to atmosphere and water,resulting in severe pollutions on environment and potential threats to human hea...Various ions and antibiotics,widely used in industry and clinical medicine,respectively,are massively discharged to atmosphere and water,resulting in severe pollutions on environment and potential threats to human health.Besides,amino acids,the primary substances for the establishment of proteins,cells and tissues,are crucial to human health.Therefore,seeking effective and practicable materials to detect aforesaid analytes is vitally meaningful.Metal-organic frameworks centered with lanthanide ions(Ln-MOFs),also known as lanthanide coordination polymers,are considered as a charming category of multi-functional hybrid crystalline materials with fascinating structures and incomparable luminescent characteristics.Benefited from their unique merits,Ln-MOFs have been largely developed as excellent luminescent sensors for fast and efficient sensing various analytes.In this review,we aim to introduce some of the recent researches between 2018 to 2022 on Ln-MOFs applied as chemical sensors for ions,antibiotics and amino acids based on luminescent quenching and enhancing effects,and provide an update and summary for the latest progresses in this field.展开更多
The direct functionalization of CAH bonds has been one of the fundamental and challenging fields in organic chemistry.In contrast with traditional chemical oxidation(mostly involving strong oxidants and expensive meta...The direct functionalization of CAH bonds has been one of the fundamental and challenging fields in organic chemistry.In contrast with traditional chemical oxidation(mostly involving strong oxidants and expensive metal complex)and photo-chemical oxidation,electrochemistry accomplishing redox processes,by employing electron as a‘‘green reagents',provides a practical and sustainable alternative strategy to effect such transformations.展开更多
Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge ...Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs.Herein,two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings(BTPS)or selenophene rings(BTPSe)are designed and synthesized as the donor cores for constructing NFAs(MQX-2 and MQX-4).It is found that replacing the sulfur atoms(MQX-2)at the outer positions of the heteroarene core with selenium atoms(MQX-4)can effectively modulate the molecular packing mode of the NFAs.The incorporation of selenium atoms induces stronger O···Se noncovalent interaction than O···S,thus promoting the formation of mixed H/J-type aggregates in MQX-4.Benefiting from more electron hopping channels,MQX-4 exhibits higher electron transport(more than 1-fold enhancement)and photovoltaic properties compared to MQX-2,which forms only H-type aggregates.展开更多
Three kinds of complexes,V_2Cu_2S_4 cubane-like,VS_4Cu_4 planar and V_3S_7 triangular dusters are obtained from a reaction system composed of(NH_4)_3VS_4,CuCl,R_2dtcNa and PhSNa.A mechanism of the formation of the pro...Three kinds of complexes,V_2Cu_2S_4 cubane-like,VS_4Cu_4 planar and V_3S_7 triangular dusters are obtained from a reaction system composed of(NH_4)_3VS_4,CuCl,R_2dtcNa and PhSNa.A mechanism of the formation of the products is suggested.The title compound is structurally characterized,showing the metal oxidation states of V(IV)+Cu(I).Also discussed are IR,UV-Vis and NMR spectra,and cyclic voltagrammetry for the V_2Cu_2S_4 clusters.展开更多
A new macrocyclic compound has been synthesized by condensation of pyridine-l-oxide-2, 6-dialdehyde with diethylenetriamine. The self-assembly behaviours were studied by X-ray diffraction. The results show that the se...A new macrocyclic compound has been synthesized by condensation of pyridine-l-oxide-2, 6-dialdehyde with diethylenetriamine. The self-assembly behaviours were studied by X-ray diffraction. The results show that the self-assembly were controlled by intermolecular hydrogen bonds and π-π stacking effects.展开更多
In general,flexible metal-organic frameworks(MOFs)change their structures via framework breathing in response to external stimuli(usually vip adsorption and desorption).Here,we show a dynamic coordination bond in a ...In general,flexible metal-organic frameworks(MOFs)change their structures via framework breathing in response to external stimuli(usually vip adsorption and desorption).Here,we show a dynamic coordination bond in a flexible MOF driving a thermo-induced diffuse phase transition occurring in a wide temperature range of 130-270 K(centered at~200 K),which enables the switching of magnetism and second-harmonic generation(SHG)responses.In specific,a solvent-free Co^(Ⅱ)-based flexible MOF Co_(2)(TPY)_(2)(BPTC)(1),bearing biphenyl-3,3',5,5'-tetracarboxylic acid(H_(4)BPTC)and 2,2':6',2''-terpyridine(TPY)ligands,exhibits a reversible thermo-responsive coordination-mode switching between five-and six-fold.This dynamic bond results in the reversible transformation between a distorted polar framework and a regular nonpolar framework,and therefore leads to the subtle change of the magnetic property and substantial change of the nonlinear optical property of 1.展开更多
Selective emitters are crucial as the key component determining the energy conversion efficiency of radioisotope thermophotovoltaic(RTPV)systems.Developing selective emitter materials with high selective emissivity,hi...Selective emitters are crucial as the key component determining the energy conversion efficiency of radioisotope thermophotovoltaic(RTPV)systems.Developing selective emitter materials with high selective emissivity,high spectral efficiency and excellent high-temperature stability can effectively improve the energy conversion efficiency and service life of RTPV systems.To adjust the selective emissivity and spectral efficiency,a series of rare earth tantalate selective emitters(Er(Ta_(1−x)Nb_(x))O_(4)(0≤x≤0.2))matching GaSb batteries were prepared by high-temperature solidstate reaction and pressureless sintering method.The as-prepared Er(Ta_(1−x)Nb_(x))O_(4)(0≤x≤0.2)ceramics exhibit high emissivity(49%–93%)in the selective band(1.40–1.60μm),high spectral efficiency(59.46%–62.12%)and excellent high-temperature stability at 1400℃.On one hand,doping Nb^(5+)into the B-site changes the crystal local structure symmetry around Er^(3+),which promotes the f–f transition of Er^(3+)and enhances the selective emission performance.On the other hand,doping Nb^(5+)ions into the B-site can alter the bandgap and oxygen vacancy concentration to suppress non-selective emissivity.Increasing the selective emissivity and reducing the non-selective emissivity is beneficial for improving the spectral efficiency of selective emitters.Hence,the selective emissivity and spectral efficiency of Er(Ta_(1−x)Nb_(x))O_(4)(0≤x≤0.2)can be effectively enhanced through compositional design,providing a new strategy for developing selective emitter materials for RTPV applications.展开更多
Organic solar cells(OSCs)have experienced remarkable performance progress up to 20%benchmark power conversion efficiency(PCE)in past years.Considering the<1%initial PCE obtained by OSC decades ago,the milestone of ...Organic solar cells(OSCs)have experienced remarkable performance progress up to 20%benchmark power conversion efficiency(PCE)in past years.Considering the<1%initial PCE obtained by OSC decades ago,the milestone of surpassing 20%efficiency is of great significance.Meanwhile,further performance promotion is urgently required for OsCs as other solution-processable photovoltaic technologies are also competitive.This review article aims to demonstrate a comprehensive summary of recent reports on OSCs with over 20%PCE,delving into key strategies including material innovations,multi-component system construction,deposition protocol optimization,solid/solvent additive engineering,as well as hole/electron transport layer development.In addition,this study identifies the next-stage scientific and technological issues that warrant greater attention.These issues are proposed to drive more prosperous research development,particularly in the field of flexible and wearable power suppliers.展开更多
文摘Polymeric cerium nitrate complex with 1,4 bis(phenylsulfinyl)butane (bphsb) [Ce(bphsb) 2(NO 3) 3] n (1) was synthesized and characterized. The crystal structure of the complex indicated that the ligand bphsb and cerium(Ⅲ) ion form a polymeric double bridge chain complex involving 18 membered macrometallocycles. Each cerium ion is coordinated by ten O atoms in a distorted 4,4 bicapped square antiprism. In the complex the disulfoxide ligand acts as bis monodentate O ligand bridging metal centers.
基金financially supported by the National Natural Science Foundation of China(Nos.22175177,21971238,22193042,21833010,22125110,22122507,21921001,and U21A2069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBS-LY-SLH024)+1 种基金The National Postdoctoral Program for Innovative Talents(No.BX2021315)the National Key Research and Development Program of China(No.2019YFA0210402)。
文摘Lead-halide perovskites exhibit outstanding performance in X-ray detection due to their intrinsic features such as high charge carrier mobility,large atomic number,and long carrier lifetime,but the toxicity of lead is regarded as the major factor hindering their development.Here,we introduce organic molecule(R)-(-)-2-methylpiperazine(R-MPz)into the bismuth-based structure to synthesize lead-free(R)-(H_(2)MPz)BiI_(5)(R-MBI).The high-quality centimeter-sized single crystals have been obtained,which show a low dark current and superior environmental stability.Particularly,the single-crystal device of R-MBI exhibits a highμτproduct up to 1.88×10^(-4)cm^(2)/V and a low trap density of 1.21×10^(10)cm^(-3).Further,the detector displays excellent detection sensitivity of 263.58μC Gy_(air)^(-1)cm^(-2)and a favorable low detection limit of 4.35μGyair/s,both of which meet the requirement for medical diagnostics.These findings shed light on the exploration of innovative bismuth-based hybrid perovskites for high-performance X-ray detection.
基金supported by the National Natural Science Foundation of China(Nos.22193042,22125110,22075285,52473283,21921001,U21A2069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBS-LY-SLH024)the Youth Innovation Promotion of Chinese Academy of Sciences(No.2020307)。
文摘Polar semiconductors,particularly the emerging polar two-dimensional(2D)halide perovskites,have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarizationgenerated photoelectric effects.However,the constraints on the organic cation's choice are still subject to limitations of polar 2D halide perovskites due to the size of the inorganic pocket between adjacent corner-sharing octahedra.Herein,a mixed spacer cation ordering strategy is employed to assemble a polar 2D halide perovskite NMAMAPb Br_(4)(NMPB,NMA is N-methylbenzene ammonium,MA is methylammonium)with alternating cation in the interlayer space.Driven by the incorporation of a second MA cation,the perovskite layer transformed from a 2D Pb_(7)Br_(24)anionic network with corner-and face-sharing octahedra to a flat 2D PbBr_(4)perovskite networks only with corner-sharing octahedra.In the crystal structure of NMPB,the asymmetric hydrogen-bonding interactions between ordered mixed-spacer cations and 2D perovskite layers give rise to a second harmonic generation response and a large polarization of 1.3μC/cm^(2).More intriguingly,the ordered 2D perovskite networks endow NMPB with excellent self-powered polarization-sensitive detection performance,showing a considerable polarization-related dichroism ratio up to 1.87.The reconstruction of an inorganic framework within a crystal through mixed cation ordering offers a new synthetic tool for templating perovskite lattices with controlled properties,overcoming limitations of conventional cation choice.
基金financially supported by the National Natural Science Foundation of China(Nos.22435005,22193042,21921001,52202194,22305105,22201284)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBSLY-SLH024)。
文摘Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.
基金Supported by the National Natural Science Foundation of China(No.21501075 and 21501076)the Natural Science Foundation of Jiangsu Province(No.BK20150226)+1 种基金Open Foundation of State Key Laboratory of Structure Chemistry(20170022)Undergraduate Students Project of Jiangsu
文摘The luminescent properties of two Eu3＋ compounds based on quinoline-2-car- boxylic acid （Hqc）, [Na2Eu2（qc）6（CH3COO）2（H2O）4].2DMF （1） and [Eu2（qc）6（H2O）6].3H2O （2）, as well as their syntheses and structures are reported. Both compounds are formed by slow evaporation at room temperature and exhibit zero dimensional dinuclear structures. It is worth mentioning that a 4.5-fold enhancement in luminescent quantum yield is achieved by reducing the nonradiative deactivation, through which the quantum yield increases remarkably to 67.62% for 1 compared with 12.18% for 2.
基金supported by the Center for Gas Separations,an Energy Frontier Research Center funded by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences(no.DESC0001015)Structural analyses were supported by the Robert A.Welch Foundation through a Welch Endowed Chair to H.-C.Z.(A-0030)+3 种基金The National Science Foundation Graduate Research Fellowship(DGE:1252521)is gratefully acknowledged.The authors also acknowledge the financial support of the U.S.Department of Energy Office of Fossil Energy,National Energy Technology Laboratory(no.DE-FE0026472)and National Science Foundation Small Business Innovation Research(NSFSBIR)under grant no.(1632486)the financial support of the Strategic Priority Research Program of the Chinese Academy of Sciences(no.XDB20000000)National Nature Science Foundation of China(no.21871266),CAS(no.QYZDY-SSWSLH025),and Youth Innovation Promotion Association CAS.
文摘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.
基金Project supported by Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Che mistry, Chinese Academy of Sciences.
文摘Each of the four vertices in chiral tetrahedral hetero-nuclear metal carbonyl clusters SFeCoM（CO）<sub>8</sub>Cp′（Ⅲ-V） is chemically different and no symmetric element could be derived from prochiral cluster SFeCo<sub>2</sub>（CO）<sub>9</sub>（Ⅰ）. Its single optically active cluster obtained by suitable method could be served as a model catalyst for asymmetric catalysis.
基金Project supported by NNSFC and the Natural Science Foundation of Fujian.
文摘A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group C2/c with a = 2.0448(3) nm, b= 1.5086(2) nm, c= 1.7923(2) nm, β=109.32(1)°. The structure of the title compound was solved by using 1 500 (I>3σ(I)) unique reflections and refined to R = 0.068. The structural features indicate the formal oxidation state of V(IV) + Ag (I), and partial charge transfer from Ag(I) to V(IV). The actions of reactants used in the reaction are discussed and a supposed formation process of the V2Ag2S4 cluster is suggested.
基金supported by the National Key Research and Development Program of China(2022YFA1502901)National Natural Science Foundation of China(22035003,22201137,and 22371137)Fundamental Research Funds for the Central Universities(63253171).
文摘Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic frameworks(HOFs),NKM-HOF-6 and NKM-HOF-7,featuring permanent microporosity.Upon treatment with hot acetone,NKM-HOF-6 undergoes a structural transformation into NKM-HOF-7,characterized by a transition from a 3D polycatenated framework to a 2D parallel displacement-stacked structure.This transformation leads to a reduction in the maximum pore size of NKM-HOF-7 and a decrease in the density of-CF_(3)groups within its channels,thereby enhancing its preferential affinity for C_(2)H_(6)over C_(2)H_(4).The adsorption capacity difference between C_(2)H_(6)and C_(2)H_(4)in NKM-HOF-7 is 11.1 cm^(3)·g^(-1),with an IAST selectivity of 1.77,surpassing the corresponding values for NKM-HOF-6(9.6 cm^(3)·g^(-1)and 1.56,respectively).Breakthrough experiments further reveal that NKM-HOF-7 achieves nearly twice the separation efficiency of NKM-HOF-6 for C_(2)H_(6)/C_(2)H_(4)(10/90,V/V)mixtures.Theoretical calculations attribute this enhanced C_(2)H_(6)affinity to the synergistic effects of optimized pore dimensions and functionalized pore surfaces in NKM-HOF-7.These findings provide critical insights for the rational design of highly efficient C_(2)H_(6)-selective adsorbents.
基金supported by the National Natural Science Foundation of China(22101047,92261109,22371280)the Natural Science Foundation of Fujian Province(2023J01219)+5 种基金the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2023-JQ06,CXZX-2022-JQ11)the XMIREM Autonomously Deployment Project(2023GG02,2023CX04)the FJIRSM Autonomously Deployment Project(CXZX-2022-GH02)the Project Funded by China Postdoctoral Science Foundation(2023M733496)the Recruitment Program of Global Youth Expertsthe Youth Innovation Promotion Association CAS(2021302)。
文摘Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks(MOFs)and covalent organic frameworks(COFs),re sulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice.The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D_(2)/H_(2)separation(~3Å).Here,we successfully modulate the poro sity of supramolecular frameworks of[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters(L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO_(4)-or Cl^(-))by controlling the duration of self-assembly processes.By simply adjusting the reaction time,we obtain three[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)supramolecular frameworks:[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)(μ^(3)-OH)_(24)(ClO_(4))L_(12))]·(Cl)_(4)·(HCO_(2))_(7)(1),[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(ClO_(4))4·(Cl)_(6)·(HCO_(2))·(H_(2)O)10(2),and[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(Cl)_(11)·(H_(2)O)12(3).The different stacking patterns of the[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters in these frameworks lead to significantly varied stabilities and porosities.Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions.In contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon desolvation.The pores of compound 1 show higher affinity to D_(2)than H_(2),and the pore aperture diameter of compound 1(~3.06Å)meets the optimal porosity for D_(2)/H_(2)separation.Consequently,compound 1 demonstrates moderate D_(2)/H_(2)separation at 77 K(retention time:~7 min/g for D_(2)/H_(2)/Ne(10/10/80 vol%)in a flow of 5 mL/min).These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.
基金supported by the Major Research Projects for Young and Middle-aged Talent of Fujian Provincial Health Commission(2021ZQNZD013)the Medical Innovation Project of Fujian Province(2021CXA043)+4 种基金the National Natural Science Foundation of China(62275050,62175031,and 22274023)the Natural Science Foundation of Fujian Province(2023J05093 and 2024J011224)the Scientific Foundation of Fuzhou Municipal Health Commission(2022-S-wt3),the Scientific Foundation of Fuzhou Municipal Health Commission(2022-S-rc1),the Scientific Foundation of Fuzhou Municipal Health Commission(2021-S-wp1)the Fujian Provincial Clinical Research Center for Hepatobiliary and Pancreatic Tumors(2020Y2013)the Fuzhou“14th Five-Year”Clinical Key Specialty(20220203)。
文摘Peroxynitrite(ONOO^(-))is a highly reactive nitrogen species that plays pivotal roles in cell signal transduction and physiological or pathological progresses.However,commonly used ONOO^(-)optical imaging probes are still hampered by high background/autofluorescence(fluorescence probe),short emission wavelength,or poor selectivity in the case of chemiluminescence.Herein,we report a facile method to prepare an activatable chemiluminescence probe(PPA-PEG)with good biocompatibility and functionality for in vivo autofluorescence-free imaging of ONOO^(-).The PPA-PEG consists of pyropheophorbide-a(PPA),a typical deep red photosensitizer that acts as both the recognition and signaling element,and 4-arm poly(ethylene glycol)(4-arm PEG),which improves the biosafety and water solubility of probe.These components can self-assemble into nanoparticles(namely PPA-PEG nanoprobe)in aqueous solution.The PPA-PEG nanoprobe showed an ultra-low chemiluminescence signal before interacting with ONOO^(-),but exhibited good selectivity,high sensitivity and a fast response toward ONOO^(-).The PPAPEG was successfully applied to image cellular ONOO^(-)changes,as well as the endogenous ONOO^(-)changes in inflammation models and subcutaneous or orthotopic hepatocellular carcinoma(HCC)tumors models in living mice.In vitro and in vivo studies verified the good detection and imaging capabilities of PPA-PEG for peroxynitrite,demonstrating suitable tissue penetration and a high signal-to-background ratio(SBR).Thus,our nanoprobe can serve as a valuable activatable chemiluminescence imaging tool for studying important peroxynitrite-related chemical and biological applications.
基金supported by the National Natural Science Foundation of China (21403240)
文摘The transition metal catalyzed C-H bond functionalization of hydrocarbons has aroused great interests in recent years due to the potential opportunity of developing novel methodologies in synthesis and chemical processes.
基金financially supported by the National Natural Science Foundation of China(21801107)the Natural Science Foundation of Shandong Province(ZR2018BB005)the Youth Innovation Team of Shandong Colleges and Universities(2019KJC027)。
文摘Various ions and antibiotics,widely used in industry and clinical medicine,respectively,are massively discharged to atmosphere and water,resulting in severe pollutions on environment and potential threats to human health.Besides,amino acids,the primary substances for the establishment of proteins,cells and tissues,are crucial to human health.Therefore,seeking effective and practicable materials to detect aforesaid analytes is vitally meaningful.Metal-organic frameworks centered with lanthanide ions(Ln-MOFs),also known as lanthanide coordination polymers,are considered as a charming category of multi-functional hybrid crystalline materials with fascinating structures and incomparable luminescent characteristics.Benefited from their unique merits,Ln-MOFs have been largely developed as excellent luminescent sensors for fast and efficient sensing various analytes.In this review,we aim to introduce some of the recent researches between 2018 to 2022 on Ln-MOFs applied as chemical sensors for ions,antibiotics and amino acids based on luminescent quenching and enhancing effects,and provide an update and summary for the latest progresses in this field.
基金supported by the National Natural Science Foundation of China(21403240)
文摘The direct functionalization of CAH bonds has been one of the fundamental and challenging fields in organic chemistry.In contrast with traditional chemical oxidation(mostly involving strong oxidants and expensive metal complex)and photo-chemical oxidation,electrochemistry accomplishing redox processes,by employing electron as a‘‘green reagents',provides a practical and sustainable alternative strategy to effect such transformations.
基金supported by the National Natural Science Foundation of China(Nos.52130306,22075287)the Program of Youth Innovation Promotion Association CAs(No.2021299).
文摘Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs.Herein,two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings(BTPS)or selenophene rings(BTPSe)are designed and synthesized as the donor cores for constructing NFAs(MQX-2 and MQX-4).It is found that replacing the sulfur atoms(MQX-2)at the outer positions of the heteroarene core with selenium atoms(MQX-4)can effectively modulate the molecular packing mode of the NFAs.The incorporation of selenium atoms induces stronger O···Se noncovalent interaction than O···S,thus promoting the formation of mixed H/J-type aggregates in MQX-4.Benefiting from more electron hopping channels,MQX-4 exhibits higher electron transport(more than 1-fold enhancement)and photovoltaic properties compared to MQX-2,which forms only H-type aggregates.
基金the National Natural Science Foundation of Chinathe Climbing Program Foundation of China
文摘Three kinds of complexes,V_2Cu_2S_4 cubane-like,VS_4Cu_4 planar and V_3S_7 triangular dusters are obtained from a reaction system composed of(NH_4)_3VS_4,CuCl,R_2dtcNa and PhSNa.A mechanism of the formation of the products is suggested.The title compound is structurally characterized,showing the metal oxidation states of V(IV)+Cu(I).Also discussed are IR,UV-Vis and NMR spectra,and cyclic voltagrammetry for the V_2Cu_2S_4 clusters.
基金Project supported by the National Natural Science Foundation of China (No. 2957106) and the Foundation of Department of Education (No. 96028424).
文摘A new macrocyclic compound has been synthesized by condensation of pyridine-l-oxide-2, 6-dialdehyde with diethylenetriamine. The self-assembly behaviours were studied by X-ray diffraction. The results show that the self-assembly were controlled by intermolecular hydrogen bonds and π-π stacking effects.
基金supported by the National Natural Science Foundation of China(92261109,22371280)the Natural Science Foundation of Fujian Province(2023J01219)+4 种基金the Project Funded by China Postdoctoral Science Foundation(2023M733496)the Recruitment Program of Global Youth Expertsthe Xiamen Institute of Rare Earth Materials(XIREM)Autonomously Deployment Project(No.2023GG02)the Fujian Institute of Research on the Structure of Matter(FJIRSM)Autonomously Deployment Project(CXZX-2022-GH02)the Youth Innovation Promotion Association CAS(2021302)。
文摘In general,flexible metal-organic frameworks(MOFs)change their structures via framework breathing in response to external stimuli(usually vip adsorption and desorption).Here,we show a dynamic coordination bond in a flexible MOF driving a thermo-induced diffuse phase transition occurring in a wide temperature range of 130-270 K(centered at~200 K),which enables the switching of magnetism and second-harmonic generation(SHG)responses.In specific,a solvent-free Co^(Ⅱ)-based flexible MOF Co_(2)(TPY)_(2)(BPTC)(1),bearing biphenyl-3,3',5,5'-tetracarboxylic acid(H_(4)BPTC)and 2,2':6',2''-terpyridine(TPY)ligands,exhibits a reversible thermo-responsive coordination-mode switching between five-and six-fold.This dynamic bond results in the reversible transformation between a distorted polar framework and a regular nonpolar framework,and therefore leads to the subtle change of the magnetic property and substantial change of the nonlinear optical property of 1.
基金supported by the National Natural Science Foundation of China(No.52402093)the Self-deployment Project Research Programs of Haixi Institutes,Chinese Academy of Sciences(No.CXZX-2023-JQ07)+3 种基金the National Key R&D Program of China(No.2022YFB3504302)the Young Elite Scientists Sponsorship Program by CAST(No.YESS20210336)the XMIREM Autonomously Deployment Project(Nos.2023GG03 and 2023CX01)the Natural Science Foundation of Xiamen(No.3502Z202472048).
文摘Selective emitters are crucial as the key component determining the energy conversion efficiency of radioisotope thermophotovoltaic(RTPV)systems.Developing selective emitter materials with high selective emissivity,high spectral efficiency and excellent high-temperature stability can effectively improve the energy conversion efficiency and service life of RTPV systems.To adjust the selective emissivity and spectral efficiency,a series of rare earth tantalate selective emitters(Er(Ta_(1−x)Nb_(x))O_(4)(0≤x≤0.2))matching GaSb batteries were prepared by high-temperature solidstate reaction and pressureless sintering method.The as-prepared Er(Ta_(1−x)Nb_(x))O_(4)(0≤x≤0.2)ceramics exhibit high emissivity(49%–93%)in the selective band(1.40–1.60μm),high spectral efficiency(59.46%–62.12%)and excellent high-temperature stability at 1400℃.On one hand,doping Nb^(5+)into the B-site changes the crystal local structure symmetry around Er^(3+),which promotes the f–f transition of Er^(3+)and enhances the selective emission performance.On the other hand,doping Nb^(5+)ions into the B-site can alter the bandgap and oxygen vacancy concentration to suppress non-selective emissivity.Increasing the selective emissivity and reducing the non-selective emissivity is beneficial for improving the spectral efficiency of selective emitters.Hence,the selective emissivity and spectral efficiency of Er(Ta_(1−x)Nb_(x))O_(4)(0≤x≤0.2)can be effectively enhanced through compositional design,providing a new strategy for developing selective emitter materials for RTPV applications.
基金the National Natural Science Foundation of China(52422313 and 52173172)the PolyU Distinguished Postdoctoral Fellowship(1-YW4C)+4 种基金the National Natural Science Foundation of China(22475133,22309119,and 52303226)financially supported by the National Natural Science Foundation of China(52403239)the Sichuan Science and Technology Program(2023YFH0085 and 2023YFH0087)the National Key Laboratory of Advanced Polymer Materials(sklpme 2024-2-15)the Technology Development Program of Jilin Province(YDZJ202201ZYTS640)。
文摘Organic solar cells(OSCs)have experienced remarkable performance progress up to 20%benchmark power conversion efficiency(PCE)in past years.Considering the<1%initial PCE obtained by OSC decades ago,the milestone of surpassing 20%efficiency is of great significance.Meanwhile,further performance promotion is urgently required for OsCs as other solution-processable photovoltaic technologies are also competitive.This review article aims to demonstrate a comprehensive summary of recent reports on OSCs with over 20%PCE,delving into key strategies including material innovations,multi-component system construction,deposition protocol optimization,solid/solvent additive engineering,as well as hole/electron transport layer development.In addition,this study identifies the next-stage scientific and technological issues that warrant greater attention.These issues are proposed to drive more prosperous research development,particularly in the field of flexible and wearable power suppliers.
