Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures ...Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures were fully characterized by IR,EI-MS and NMR.The catalytic systems,prepared in situ from the multidentate ligands and iridium（I） complexes,showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution,leading to corresponding optical alcohol with up to 75%ee.展开更多
To search for more better sensitizer of organic solar cell, a series of multidentate squaraines (Sq1~6) were synthesized, the structures were determined by elemental analysis, IR, UV-vis, 1H NMR and MS spectroscopies....To search for more better sensitizer of organic solar cell, a series of multidentate squaraines (Sq1~6) were synthesized, the structures were determined by elemental analysis, IR, UV-vis, 1H NMR and MS spectroscopies. The squaraines have good solubility in polar solvents such as EtOH, CH3COCH3, CHCl3,etc. as well as strong absorption band over 600~700 nm spectral range.展开更多
Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hy...Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.展开更多
Sb_(2)S_(3)is a promising candidate for the flexible solar cells or the top subcells in tandem solar cells due to its wide-bandgap,less toxic,acceptable cost and progressive power conversion efficiency(PCE).However,th...Sb_(2)S_(3)is a promising candidate for the flexible solar cells or the top subcells in tandem solar cells due to its wide-bandgap,less toxic,acceptable cost and progressive power conversion efficiency(PCE).However,the poor quality and high trap states of Sb_(2)S_(3)films limit the device performance further enhancement.Herein,we adopt a multidentate ionic liquid,tetramethylammonium hexafluorophosphate([TMA][PF_(6)])as a novel additive to address this issue.The octahedral[PF_(6)]~-contains six different oriented fluorine atoms with the lone pair electrons,which could coordinate with Sb atoms due to the multidentate anchoring.Thus,the high-quality Sb_(2)S_(3)film with low trap states has been achieved.Moreover,the Fermi level of the Sb_(2)S_(3)film has been upshifted,thereby showing an effective charge transfer.As a result,all photovoltaic parameters of the optimized Sb_(2)S_(3)devices are obviously enhanced,boosting the final PCE from 4.43(control device)to 6.83%.Our study about the multidentate anchoring is manifested to be an effective method to enhance the Sb_(2)S_(3)device performance.展开更多
A synthetic route to flapping poly-Lewis acids(PLAs)based on dibenzocyclooctatetraene was developed.The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases(LB)including drugs was...A synthetic route to flapping poly-Lewis acids(PLAs)based on dibenzocyclooctatetraene was developed.The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases(LB)including drugs was investigated in detail.By using different monodentate LBs,the different effective Lewis acidities(eLA)of the respective pairings were determined and compared with each other.The reaction with multidentate LBs yielded a range of adducts,which were analysed in solution by NMR methods,including DOSY NMR spectroscopy,and in the solid state by X-ray diffraction.The adducts include specific oligomers,and coordination polymers constructed via B-P,Al-P and Al-N interactions.The solid-state structures of these coordination polymers have been determined.The results of complexation of bidentate LB by the tetradentate PLA show that LB is preferentially chelated in the binding pockets,which does not impede the flapping movement during chelating complexation.This phenomenon can be attributed to a reduction in entropy when this flapping motion is lost.The aluminium containing PLAs were observed to form a complex with two caffeine molecules,exhibiting remarkable preference for oxygen functions.In contrast,the reaction with theobromine resulted in the degradation of the PLAs due to the presence of acidic protons in theobromine,leading to the formation of a dimeric aluminium containing theobromine derivative.These findings demonstrate the interaction of PLAs with drugs.They provide a foundation for the advancement of PLAs with a tuneable orientation of Lewis acidic functions.展开更多
The non-radiative recombination loss at the interface between a perovskite layer and hole transport layer is one of the main sources of energy loss in perovskite solar cells(PSCs).Non-radiative recombination caused by...The non-radiative recombination loss at the interface between a perovskite layer and hole transport layer is one of the main sources of energy loss in perovskite solar cells(PSCs).Non-radiative recombination caused by surface defects greatly limits further improvement of power conversion efficiency(PCE).Interfacial passivation is one of the commonly used methods to improve PCE,but traditional passivation methods often involve single-point coordination,and their passivation effect is limited.In this study,we used a multi-site binding passivation method,introducing diethyl 2,6-pyridinedicarboxylate(DIP)as a passivation layer at the interface between the perovskite and the hole transport layer.The ester and pyridinium groups can interact effectively with uncoordinated Pb^(2+),and this multidentate chelation effect can repair various defects,improve crystallization,and promote interfacial carrier transfer.As a result,the optimized device achieves an efficiency of 23.68%.Additionally,due to the hydrophobicity of DIP,the device exhibits excellent humidity stability,maintaining 89.40%of its initial PCE after 550 hours at a relative humidity of 65±5%.展开更多
The organics containing multiple Lewis base groups are commonly used as additives to build high-quality perovskite film to improve the performance of perovskite solar cells(PSCs).However,the relationship between the s...The organics containing multiple Lewis base groups are commonly used as additives to build high-quality perovskite film to improve the performance of perovskite solar cells(PSCs).However,the relationship between the synergistic effects of the multifunctional groups induced by the molecular configuration of the additives and their effect remains to be probed.Herein,the isomeric additives of 2-amino-5-iodobenzoic acid(O-IA)and 4-amino-3-iodobenzoic acid(P-IA)are selected to in detail explore the impact of molecular conformation on their modulation of perovskite film quality.Theoretical and experimental analyses reveal that compared to the adsorption effect formed by the para-position–C=O and–NH_(2)groups in P-IA with the adjacent lead ions in the perovskite lattice,the multidentate chelating constituted by the ortho-position–C=O and–NH_(2)groups in O-IA with the single lead ions results in its a stronger bonding with the perovskite precursor and the(110)plane of perovskite,which modulates the crystallization and preferential growth of the perovskite film.Additionally,the stronger intermolecular interactions of O-IA and its bonding with perovskite than P-IA more effectively release the strain of perovskite film.Therefore,the O-IA-treated perovskite film exhibits substantially enhanced oriented crystallization,reduced residual strain and defect states,and improved energy level matching.As a result,the unencapsulated air-processed carbon-based PSCs with O-IA achieve a champion power conversion efficiency of 17.50%and superior stability after 480 h of aging in air at 50℃,20%relative humidity(RH)and at 25℃,85%RH.展开更多
Efficient use of energy is a pressing issue.Improvement of chemical processes is currently an important target for energy efficiency.Although chemical processes are independent of pathways with respect to the final en...Efficient use of energy is a pressing issue.Improvement of chemical processes is currently an important target for energy efficiency.Although chemical processes are independent of pathways with respect to the final energy output or consumption,the application of catalysts can reduce involved activation energies considerably and therefore save large amounts of energy.展开更多
By using a flexible multidentate ligand,bis（2-hydroxyethyl）iminotris（hydroxyhydroxylmethy）methane（＇bis-tris＇：H5L）,the title complex {[Na（H6L）2]2}n·nV10O28（1） has been successfully synthesized under s...By using a flexible multidentate ligand,bis（2-hydroxyethyl）iminotris（hydroxyhydroxylmethy）methane（＇bis-tris＇：H5L）,the title complex {[Na（H6L）2]2}n·nV10O28（1） has been successfully synthesized under self-assembly condition and characterized by IR spectroscopy,elemental analysis,PXRD and single-crystal X-ray diffraction.The crystal structure belongs to an orthorhombic system,space group Cmca with a = 23.752（2）,b = 13.5360（8）,c = 18.5377（11） ,V = 5960.1（7）,Z = 8,Dc = 2.055 g/cm3,F（000） = 3744,μ = 1.630 mm-1,the final R = 0.0283 and wR = 0.0759 for 3353 observed reflections with I 〉 2σ（I）.This complex consists of decavanadate [V10O28]6-motifs as counter anions intercalated with one-dimensiond chains of the composition [Na（H6L）2]n3n＋.And significant intermolecular O-H…O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.展开更多
A novel 1,2,3-triazolyl-containing ligand （H2L） with long donor arms extending from the central pyridyl linker was synthesized by click cycloaddition of 2,6-bis（azidomethyl）pyri- line and 2-（（prop-2-yn-1-yl（pyr...A novel 1,2,3-triazolyl-containing ligand （H2L） with long donor arms extending from the central pyridyl linker was synthesized by click cycloaddition of 2,6-bis（azidomethyl）pyri- line and 2-（（prop-2-yn-1-yl（pyridin-2-ylmethyl）amino）methyl）phenol. Further treatment of the igand H2L with zinc（II） perchlorate in the presence of triethylaminc, followed by anion exchange vith Na[BPh4], provided a dinuclear zinc（II） complex [Zn2L][BPh4]E-2DMF （1）. Complex 1 crystallizes in monoclinic, space group P21 with a = 10.4873（4）, b = 14.9078（5）, c = 25.8620（9） A, = 94.566（2）°, V = 4030.5（2） A3, Z = 2,μ= 0.657 mm-1, Dc = 1.324 Mg/m3, T = 296（2） K, C93H91N13B2O4Zn2, Mr = 1607.19, F（000） = 1684, S = 0.958, R = 0.0271 and wR = 0.0607. In the tructurc of cation, the phenolate oxygen atoms of ligand act as the bridging nodes to form a hombic Zn2（OAr）2 core.展开更多
The crystal engineering of octacyanidomolybdate(Ⅳ)ions and copper(Ⅱ)complexes with two types of chelating ligands:multidentate blocking ligand,tren=(tris(2 aminoethyl)amine),and bidentate ligand capable of forming u...The crystal engineering of octacyanidomolybdate(Ⅳ)ions and copper(Ⅱ)complexes with two types of chelating ligands:multidentate blocking ligand,tren=(tris(2 aminoethyl)amine),and bidentate ligand capable of forming unusual organic bridges,tn=1,3-diaminopropane,resulted in the formation of{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·7.5H2O(1)and{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·{[Cu(tren)]2[Mo(CN)8]}·9H2O(2).The crystal structure of 1 comprises isolated anions[Mo(CN)8]4-wrapped with charge-compensating units{[Cu(tren)]2(μ-tn)}^(4+)stabilised by extensive H-bond networks.Compound 2 forms alternating layers consisting of the same ions as 1 and neutral cyanido-bridged V-shaped trinuclear molecules{[Cu(tren)]2[Mo(CN)8]}.Additionally,two previously reported V-shaped trinuclear reference systems were synthesised:[Cu(tn)2]2[Mo(CN)_(8)]·2H_(2)O(3)and[Cu(tren)]2[Mo(CN)8]·5.25H2O(4).UV–Vis–NIR absorption spectroscopy,supported by quantum chemical calculations(DFT and TD-DFT),confirmed the presence of Mo(Ⅳ)to Cu(Ⅱ)charge transfer bands centred on trinuclear molecules(2–4)and their absence for the ionic sample 1 without CN^(-)-bridges.Additionally,detailed descriptions of the energy level diagrams of 1–4 with the frontier molecular orbitals and possible optical transitions were made.Magnetic studies indicated paramagnetic behaviour with weak antiferromagnetic interactions at low temperature.Finally,photomagnetic studies of 1–3 showed the increase of magnetization after irradiation with 473 and 410 nm light at 10 K.Comparative analysis of all data suggests that the photomagnetic effect in 1 is well described by the lightinduced excited spin-state trapping(LIESST)effect in the Mo(Ⅳ)centre,while other cyanido-bridged compounds prefer the metal-to-metal charge transfer with minor contribution of LIESST effects.展开更多
Laser-sensitive primary explosives(LSPEs)have long been a focus of attention as the material foundation for safer and more efficient laser-initiation technology.However,LSPEs often have poor safety due to their struct...Laser-sensitive primary explosives(LSPEs)have long been a focus of attention as the material foundation for safer and more efficient laser-initiation technology.However,LSPEs often have poor safety due to their structural characteristics,which greatly limits the development and application of laser initiating technology.In this work,we introduced the concept of multidentate chelates into LSPEs and innovatively propose the concept of energetic quadridentate chelates.To achieve this highly creative idea,we synthesized an energetic flexible chelating ligand,namely,1,2-bis(3-nitroamino-1,2,4-triazol-5-yl)ethane(BNATE),and prepared a novel metal quadridentate chelate,namely,[Cu(BNATE)·2H_(2)O](1),by chelating it with Cu^(2+).Through a series of tests,including X-ray single-crystal diffraction analysis,thermogravimetric analysis,and differential scanning calorimetry(TG-DSC),and evaluation of the safety and detonation performance,it was proven that this compound adhered to the high stability characteristics of the chelate,and its safety and detonation performance were superior to previous LSPEs.Moreover,through laserinitiation experiments,it was determined that the compound had excellent photosensitivity and a lower laser-initiation threshold.To explain the reason why the chelate structure is specifically sensitive to a laser,diffuse reflection ultraviolet and TD-DFT simulations were conducted,which not only demonstrated experimentally that chelation had a good enhancement effect on the laser photosensitivity but also confirmed the mode of electron transfer in the quadridentate chelate structure.展开更多
A modular multidentate ligand scaffold is crafted by strategically incorporating three pyridines(NPy)and three imines along with a pendant tertiary amine(N_(tert))around a mononuclear copper centre.This unique design ...A modular multidentate ligand scaffold is crafted by strategically incorporating three pyridines(NPy)and three imines along with a pendant tertiary amine(N_(tert))around a mononuclear copper centre.This unique design leads to the generation of a molecular copper complex C1 with a dynamically adaptive coordination environment,where multiple proton and electron movements can be accommodated.Complex C1 demonstrates rapid hydrogen generation from water across a wide pH range(pH 1.0-7.0),with a markedly enhanced catalytic performance under acidic conditions.At pH 1.0,C1 achieves high turnover numbers(TONs)of 1014±10 within 1 hour and 2980±20 over 3 hours.In operando spectroelectrochemical investigations,in conjunction with density functional theory(DFT)calculations,reveal a unique pH-dependent structural flexibility of the ligand scaffold around the Cu centre in C1.In near-neutral to slightly acidic media(pH 3.0-7.0),the protonation of an NPy group(pKa1∼11.6)following its cleavage from the Cu linkage provides the primary protonation site,which is essential for Cu-complex-driven H_(2) production catalysis.The N_(tert) group(pK_(a2)∼2.8),positioned in the outer coordination sphere of Cu,becomes involved under highly acidic conditions(pH<3.0).Here,this pendant amine acts as the initial protonation site and alters the course of the catalysis by unleashing an energetically downhill reaction pathway consisting of spontaneous electron and proton transfer steps.This pH-specific participation of the pendant N_(tert) functionality is key for the escalated HER activity by C1 under strongly acidic conditions,which is rarely observed for Cu-based molecular complexes.Complementary surface and solution-phase analyses confirm the molecular integrity of the complex,supporting a homogeneous catalytic mechanism operative throughout the hydrogen evolution process.展开更多
Two trinuclear complexes,[Cu^(II)_(3)(L)_(2)](BF_(4))_(2)(1)and[Ni~(II)_(3)(L)_(2)(MeOH)_(4)](BF_(4))_(2)(2),supported by the multidentate ligand L^(2-)(H_(2)L=5,5’-pyridyl-3,3’-bi-1H-pyrazole)were obtained and thei...Two trinuclear complexes,[Cu^(II)_(3)(L)_(2)](BF_(4))_(2)(1)and[Ni~(II)_(3)(L)_(2)(MeOH)_(4)](BF_(4))_(2)(2),supported by the multidentate ligand L^(2-)(H_(2)L=5,5’-pyridyl-3,3’-bi-1H-pyrazole)were obtained and their structures determined.Both complexes have linear trinuclear structures composed of two ligands and three metal ions.Cryomagnetic studies reveal that both complexes show intramolecular antiferromagnetic interactions between the metal ions.展开更多
Colloidal all-inorganic perovskite nanocrystals(PNCs),possessing unique optical properties,have attracted considerable attention in the field of semiconductor nanocrystals(NCs),but their application is hindered by the...Colloidal all-inorganic perovskite nanocrystals(PNCs),possessing unique optical properties,have attracted considerable attention in the field of semiconductor nanocrystals(NCs),but their application is hindered by the stability issue resulting partly from dynamic capping ligand binding.Herein,we report a simple method for the synthesis of all-inorganic cesium lead-based(CsPbX3)NCs with enhanced structural stability and photoluminescence quantum yield.Aluminum distearate(AlDS)was introduced into the preparation of CsPbX3 NCs,on the basis that the surface defects of CsPbX3 NCs are passivated to form a protective layer on the CsPbX3 NC surface simultaneously.Benefiting from surface modification,the resistance of the CsPbX3 NC dispersion against ethanol,ultraviolet irradiation,and heat treatment was enhanced effectively.Moreover,the photoluminescence intensity and stability of the AlDS–modified NC-based films displayed functional superiority to those of pristine NC-based films.展开更多
基金the National Natural Science Foundation of China(Nos20423002 and 20703034)Natural Science Foundation of Fujian Province of China(No2008J0235) for the financial support of this work
文摘Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures were fully characterized by IR,EI-MS and NMR.The catalytic systems,prepared in situ from the multidentate ligands and iridium（I） complexes,showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution,leading to corresponding optical alcohol with up to 75%ee.
文摘To search for more better sensitizer of organic solar cell, a series of multidentate squaraines (Sq1~6) were synthesized, the structures were determined by elemental analysis, IR, UV-vis, 1H NMR and MS spectroscopies. The squaraines have good solubility in polar solvents such as EtOH, CH3COCH3, CHCl3,etc. as well as strong absorption band over 600~700 nm spectral range.
文摘Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.
基金financially supported by the Basic Research Fund for Free Exploration in Shenzhen(No.JCYJ20180306171402878)the National Natural Science Foundation of China(No.52072228,51571166 and 21603175)the Fundamental Research Funds for the Central Universities(No.3102019JC005)。
文摘Sb_(2)S_(3)is a promising candidate for the flexible solar cells or the top subcells in tandem solar cells due to its wide-bandgap,less toxic,acceptable cost and progressive power conversion efficiency(PCE).However,the poor quality and high trap states of Sb_(2)S_(3)films limit the device performance further enhancement.Herein,we adopt a multidentate ionic liquid,tetramethylammonium hexafluorophosphate([TMA][PF_(6)])as a novel additive to address this issue.The octahedral[PF_(6)]~-contains six different oriented fluorine atoms with the lone pair electrons,which could coordinate with Sb atoms due to the multidentate anchoring.Thus,the high-quality Sb_(2)S_(3)film with low trap states has been achieved.Moreover,the Fermi level of the Sb_(2)S_(3)film has been upshifted,thereby showing an effective charge transfer.As a result,all photovoltaic parameters of the optimized Sb_(2)S_(3)devices are obviously enhanced,boosting the final PCE from 4.43(control device)to 6.83%.Our study about the multidentate anchoring is manifested to be an effective method to enhance the Sb_(2)S_(3)device performance.
基金funded by the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)grant MI 477/39-1,project no.424957011the Regional Computing Centre of the University of Cologne(RRZK)for providing computing time and support on the DFG-funded(Funding number:INST 216/512/1FUGG)HPC system CHEOPS.
文摘A synthetic route to flapping poly-Lewis acids(PLAs)based on dibenzocyclooctatetraene was developed.The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases(LB)including drugs was investigated in detail.By using different monodentate LBs,the different effective Lewis acidities(eLA)of the respective pairings were determined and compared with each other.The reaction with multidentate LBs yielded a range of adducts,which were analysed in solution by NMR methods,including DOSY NMR spectroscopy,and in the solid state by X-ray diffraction.The adducts include specific oligomers,and coordination polymers constructed via B-P,Al-P and Al-N interactions.The solid-state structures of these coordination polymers have been determined.The results of complexation of bidentate LB by the tetradentate PLA show that LB is preferentially chelated in the binding pockets,which does not impede the flapping movement during chelating complexation.This phenomenon can be attributed to a reduction in entropy when this flapping motion is lost.The aluminium containing PLAs were observed to form a complex with two caffeine molecules,exhibiting remarkable preference for oxygen functions.In contrast,the reaction with theobromine resulted in the degradation of the PLAs due to the presence of acidic protons in theobromine,leading to the formation of a dimeric aluminium containing theobromine derivative.These findings demonstrate the interaction of PLAs with drugs.They provide a foundation for the advancement of PLAs with a tuneable orientation of Lewis acidic functions.
基金supported by the National Key R&D Program of China(2022YFB4200500)the Key Research and Development Plan Project of Anhui Province(2022h11020014)+4 种基金the National Natural Science Foundation of China(52302237)and the Collaborative Innovation Program of Hefei Science Center,CAS(2022HSC-CIP006)the CASHIPS Director’s Fund(YZJJ201902 and YZJJZX202018)the Anhui Provincial Natural Science Foundation(2408085MB029)the Anhui Postdoctoral Scientific Research Program Foundation(2024B811)the Natural Science Foundation of Hebei Province of China(B2024402018).
文摘The non-radiative recombination loss at the interface between a perovskite layer and hole transport layer is one of the main sources of energy loss in perovskite solar cells(PSCs).Non-radiative recombination caused by surface defects greatly limits further improvement of power conversion efficiency(PCE).Interfacial passivation is one of the commonly used methods to improve PCE,but traditional passivation methods often involve single-point coordination,and their passivation effect is limited.In this study,we used a multi-site binding passivation method,introducing diethyl 2,6-pyridinedicarboxylate(DIP)as a passivation layer at the interface between the perovskite and the hole transport layer.The ester and pyridinium groups can interact effectively with uncoordinated Pb^(2+),and this multidentate chelation effect can repair various defects,improve crystallization,and promote interfacial carrier transfer.As a result,the optimized device achieves an efficiency of 23.68%.Additionally,due to the hydrophobicity of DIP,the device exhibits excellent humidity stability,maintaining 89.40%of its initial PCE after 550 hours at a relative humidity of 65±5%.
基金financial support from the National Natural Science Foundation of China(52472259,22179051)the Natural Science Foundation of Shandong Province(ZR2021ME037)+1 种基金the Special Fund of Taishan Scholar Program of Shandong Province(tsqnz20221141)the Foundation of Key Laboratory of Advanced Technique&Preparation for Renewable Energy Materials,Ministry of Education,Yunnan Normal University(OF2022-02)。
文摘The organics containing multiple Lewis base groups are commonly used as additives to build high-quality perovskite film to improve the performance of perovskite solar cells(PSCs).However,the relationship between the synergistic effects of the multifunctional groups induced by the molecular configuration of the additives and their effect remains to be probed.Herein,the isomeric additives of 2-amino-5-iodobenzoic acid(O-IA)and 4-amino-3-iodobenzoic acid(P-IA)are selected to in detail explore the impact of molecular conformation on their modulation of perovskite film quality.Theoretical and experimental analyses reveal that compared to the adsorption effect formed by the para-position–C=O and–NH_(2)groups in P-IA with the adjacent lead ions in the perovskite lattice,the multidentate chelating constituted by the ortho-position–C=O and–NH_(2)groups in O-IA with the single lead ions results in its a stronger bonding with the perovskite precursor and the(110)plane of perovskite,which modulates the crystallization and preferential growth of the perovskite film.Additionally,the stronger intermolecular interactions of O-IA and its bonding with perovskite than P-IA more effectively release the strain of perovskite film.Therefore,the O-IA-treated perovskite film exhibits substantially enhanced oriented crystallization,reduced residual strain and defect states,and improved energy level matching.As a result,the unencapsulated air-processed carbon-based PSCs with O-IA achieve a champion power conversion efficiency of 17.50%and superior stability after 480 h of aging in air at 50℃,20%relative humidity(RH)and at 25℃,85%RH.
基金The National Natural Science Foundation of China(22078317)。
文摘Efficient use of energy is a pressing issue.Improvement of chemical processes is currently an important target for energy efficiency.Although chemical processes are independent of pathways with respect to the final energy output or consumption,the application of catalysts can reduce involved activation energies considerably and therefore save large amounts of energy.
基金supported by 973 Program (2011CB932504), NNSFC (20971121)NSF for Young Scientists of China (20801056)NSF of Fujian Province
文摘By using a flexible multidentate ligand,bis（2-hydroxyethyl）iminotris（hydroxyhydroxylmethy）methane（＇bis-tris＇：H5L）,the title complex {[Na（H6L）2]2}n·nV10O28（1） has been successfully synthesized under self-assembly condition and characterized by IR spectroscopy,elemental analysis,PXRD and single-crystal X-ray diffraction.The crystal structure belongs to an orthorhombic system,space group Cmca with a = 23.752（2）,b = 13.5360（8）,c = 18.5377（11） ,V = 5960.1（7）,Z = 8,Dc = 2.055 g/cm3,F（000） = 3744,μ = 1.630 mm-1,the final R = 0.0283 and wR = 0.0759 for 3353 observed reflections with I 〉 2σ（I）.This complex consists of decavanadate [V10O28]6-motifs as counter anions intercalated with one-dimensiond chains of the composition [Na（H6L）2]n3n＋.And significant intermolecular O-H…O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.
基金Financially supported by the Education Department of Jiangxi Province(GJJ13106)
文摘A novel 1,2,3-triazolyl-containing ligand （H2L） with long donor arms extending from the central pyridyl linker was synthesized by click cycloaddition of 2,6-bis（azidomethyl）pyri- line and 2-（（prop-2-yn-1-yl（pyridin-2-ylmethyl）amino）methyl）phenol. Further treatment of the igand H2L with zinc（II） perchlorate in the presence of triethylaminc, followed by anion exchange vith Na[BPh4], provided a dinuclear zinc（II） complex [Zn2L][BPh4]E-2DMF （1）. Complex 1 crystallizes in monoclinic, space group P21 with a = 10.4873（4）, b = 14.9078（5）, c = 25.8620（9） A, = 94.566（2）°, V = 4030.5（2） A3, Z = 2,μ= 0.657 mm-1, Dc = 1.324 Mg/m3, T = 296（2） K, C93H91N13B2O4Zn2, Mr = 1607.19, F（000） = 1684, S = 0.958, R = 0.0271 and wR = 0.0607. In the tructurc of cation, the phenolate oxygen atoms of ligand act as the bridging nodes to form a hombic Zn2（OAr）2 core.
基金supported in part by a JSPS Grant-in-Aid for Scientific Research(A)(Grant Number JP20H00369)a Grantin-Aid for Scientific Research on Innovative Area Soft Crystals(Area No.2903,JP17H06367)+4 种基金Grant-in-Aid for Specially Promoted Research(Grant Number JP15H05697)IM–LED LIA(CNRS)and CNRS-University of Tokyo“Excellence Science”Joint Research ProgramWe also acknowledge the Cryogenic Research Center,The University of Tokyo,the Center for Nano Lithography&Analysis,The University of Tokyo supported by MEXT,and the MEXT Quantum Leap Flagship Program(Grant Number JPMXS0118068681)for supportK.K.is grateful for a Grant in-Aid for JSPS fellows(Grant Number JP20J20245)O.S.is grateful for JSPS KAKENHI Grant Number JP21K14582.
文摘The crystal engineering of octacyanidomolybdate(Ⅳ)ions and copper(Ⅱ)complexes with two types of chelating ligands:multidentate blocking ligand,tren=(tris(2 aminoethyl)amine),and bidentate ligand capable of forming unusual organic bridges,tn=1,3-diaminopropane,resulted in the formation of{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·7.5H2O(1)and{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·{[Cu(tren)]2[Mo(CN)8]}·9H2O(2).The crystal structure of 1 comprises isolated anions[Mo(CN)8]4-wrapped with charge-compensating units{[Cu(tren)]2(μ-tn)}^(4+)stabilised by extensive H-bond networks.Compound 2 forms alternating layers consisting of the same ions as 1 and neutral cyanido-bridged V-shaped trinuclear molecules{[Cu(tren)]2[Mo(CN)8]}.Additionally,two previously reported V-shaped trinuclear reference systems were synthesised:[Cu(tn)2]2[Mo(CN)_(8)]·2H_(2)O(3)and[Cu(tren)]2[Mo(CN)8]·5.25H2O(4).UV–Vis–NIR absorption spectroscopy,supported by quantum chemical calculations(DFT and TD-DFT),confirmed the presence of Mo(Ⅳ)to Cu(Ⅱ)charge transfer bands centred on trinuclear molecules(2–4)and their absence for the ionic sample 1 without CN^(-)-bridges.Additionally,detailed descriptions of the energy level diagrams of 1–4 with the frontier molecular orbitals and possible optical transitions were made.Magnetic studies indicated paramagnetic behaviour with weak antiferromagnetic interactions at low temperature.Finally,photomagnetic studies of 1–3 showed the increase of magnetization after irradiation with 473 and 410 nm light at 10 K.Comparative analysis of all data suggests that the photomagnetic effect in 1 is well described by the lightinduced excited spin-state trapping(LIESST)effect in the Mo(Ⅳ)centre,while other cyanido-bridged compounds prefer the metal-to-metal charge transfer with minor contribution of LIESST effects.
基金financial support from the National Natural Science Foundation of China(21975232).
文摘Laser-sensitive primary explosives(LSPEs)have long been a focus of attention as the material foundation for safer and more efficient laser-initiation technology.However,LSPEs often have poor safety due to their structural characteristics,which greatly limits the development and application of laser initiating technology.In this work,we introduced the concept of multidentate chelates into LSPEs and innovatively propose the concept of energetic quadridentate chelates.To achieve this highly creative idea,we synthesized an energetic flexible chelating ligand,namely,1,2-bis(3-nitroamino-1,2,4-triazol-5-yl)ethane(BNATE),and prepared a novel metal quadridentate chelate,namely,[Cu(BNATE)·2H_(2)O](1),by chelating it with Cu^(2+).Through a series of tests,including X-ray single-crystal diffraction analysis,thermogravimetric analysis,and differential scanning calorimetry(TG-DSC),and evaluation of the safety and detonation performance,it was proven that this compound adhered to the high stability characteristics of the chelate,and its safety and detonation performance were superior to previous LSPEs.Moreover,through laserinitiation experiments,it was determined that the compound had excellent photosensitivity and a lower laser-initiation threshold.To explain the reason why the chelate structure is specifically sensitive to a laser,diffuse reflection ultraviolet and TD-DFT simulations were conducted,which not only demonstrated experimentally that chelation had a good enhancement effect on the laser photosensitivity but also confirmed the mode of electron transfer in the quadridentate chelate structure.
基金the experimental facility and financial support provided by the Indian Institute of Technology Bombay(IITB).N.A.S.would like to thank UGC for the fellowship[Ref no.:96/(CSIR-UGC NET JUNE 2019)]A.D.would like to thank the support provided by the Department of Science and Technology,Science and Engineering Research Board(DST-SERB)+1 种基金India,for the core research grant(CRG/2020/001239)We gratefully acknowledge National Center for Advanced Electron-Spin Resonance Spectroscopy(ACERT)for Electron Paramagnetic Resonance(EPR)under grant numbers R24GM146107 and R35GM148272.
文摘A modular multidentate ligand scaffold is crafted by strategically incorporating three pyridines(NPy)and three imines along with a pendant tertiary amine(N_(tert))around a mononuclear copper centre.This unique design leads to the generation of a molecular copper complex C1 with a dynamically adaptive coordination environment,where multiple proton and electron movements can be accommodated.Complex C1 demonstrates rapid hydrogen generation from water across a wide pH range(pH 1.0-7.0),with a markedly enhanced catalytic performance under acidic conditions.At pH 1.0,C1 achieves high turnover numbers(TONs)of 1014±10 within 1 hour and 2980±20 over 3 hours.In operando spectroelectrochemical investigations,in conjunction with density functional theory(DFT)calculations,reveal a unique pH-dependent structural flexibility of the ligand scaffold around the Cu centre in C1.In near-neutral to slightly acidic media(pH 3.0-7.0),the protonation of an NPy group(pKa1∼11.6)following its cleavage from the Cu linkage provides the primary protonation site,which is essential for Cu-complex-driven H_(2) production catalysis.The N_(tert) group(pK_(a2)∼2.8),positioned in the outer coordination sphere of Cu,becomes involved under highly acidic conditions(pH<3.0).Here,this pendant amine acts as the initial protonation site and alters the course of the catalysis by unleashing an energetically downhill reaction pathway consisting of spontaneous electron and proton transfer steps.This pH-specific participation of the pendant N_(tert) functionality is key for the escalated HER activity by C1 under strongly acidic conditions,which is rarely observed for Cu-based molecular complexes.Complementary surface and solution-phase analyses confirm the molecular integrity of the complex,supporting a homogeneous catalytic mechanism operative throughout the hydrogen evolution process.
基金supported by a Grant-in-Aid for Scientific Research on Innovative Areas(“Coordination Programming”Area 2107,no.21108006)the Ministry of Education,Culture,Sports,Science and Technology,Japan,and by a Grant-in-Aid for Scientific Research(no.25248014)from the Japan Society for the Promotion of Science(JSPS).
文摘Two trinuclear complexes,[Cu^(II)_(3)(L)_(2)](BF_(4))_(2)(1)and[Ni~(II)_(3)(L)_(2)(MeOH)_(4)](BF_(4))_(2)(2),supported by the multidentate ligand L^(2-)(H_(2)L=5,5’-pyridyl-3,3’-bi-1H-pyrazole)were obtained and their structures determined.Both complexes have linear trinuclear structures composed of two ligands and three metal ions.Cryomagnetic studies reveal that both complexes show intramolecular antiferromagnetic interactions between the metal ions.
基金the National Natural Science Foundation of China(grant nos.21771063 and 21975075)the State Key Research Development Program of China(grant no.2016YFA0204200)+1 种基金the Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03)the Programme of Introducing Talents of Discipline to Universities(B16017).
文摘Colloidal all-inorganic perovskite nanocrystals(PNCs),possessing unique optical properties,have attracted considerable attention in the field of semiconductor nanocrystals(NCs),but their application is hindered by the stability issue resulting partly from dynamic capping ligand binding.Herein,we report a simple method for the synthesis of all-inorganic cesium lead-based(CsPbX3)NCs with enhanced structural stability and photoluminescence quantum yield.Aluminum distearate(AlDS)was introduced into the preparation of CsPbX3 NCs,on the basis that the surface defects of CsPbX3 NCs are passivated to form a protective layer on the CsPbX3 NC surface simultaneously.Benefiting from surface modification,the resistance of the CsPbX3 NC dispersion against ethanol,ultraviolet irradiation,and heat treatment was enhanced effectively.Moreover,the photoluminescence intensity and stability of the AlDS–modified NC-based films displayed functional superiority to those of pristine NC-based films.
