Solvothermal reactions of Zn(NO3)2·6H20 with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional (3D) hereto-metallic inorganic-organic hybrid framework [ZnK2(m-BDC)f...Solvothermal reactions of Zn(NO3)2·6H20 with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional (3D) hereto-metallic inorganic-organic hybrid framework [ZnK2(m-BDC)ffH20)2]n (1, m-H2BDC = benzene-l,3-dicarboxylic acid). The crystal was characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction analysis. Complex 1 is of orthogonal crystal system, acentric space group Cmc2j with a = 19.764(6), b = 19.948(6), c = 12.039(4) A, V = 4746(3) A3, Z = 4, C32H20019KaZn2, Mr = 995.66, Dc= 1.393 g/cm3, F(000) = 2000 andp = 1.426 mm-1. The final R = 0.0761 and wR = 0.1841. The crystal exhibits remarkable blue luminescence emissions with high quantum yield of 56.02% and displays modest powder SHG efficiency of about 0.7 times that produced by a potassium dihydrogen phosphate (KDP) powder. In addition, it also exhibits potential ferroelectric property.展开更多
Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien,...Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13) and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.展开更多
A novel heterometallic complex,[Zn4Ni(OH)2(btec)2(titb)2(H2O)2]·2H2O(1)(H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trime-thylbenzene),has been hydrothermal...A novel heterometallic complex,[Zn4Ni(OH)2(btec)2(titb)2(H2O)2]·2H2O(1)(H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trime-thylbenzene),has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817(10),b=11.878(11),c=14.569(14),α=71.762(12),β=76.122(13),γ=71.493(13)°,V=1665(3)3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F(000)=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections(Ⅰ 2σ(Ⅰ)).In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.展开更多
A new heterometallic complex {[Cu(pic)2(H2O)2][Cd2(Hdipic)2(H2O)2Cl2]}n (Mr = 1007.73) has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes...A new heterometallic complex {[Cu(pic)2(H2O)2][Cd2(Hdipic)2(H2O)2Cl2]}n (Mr = 1007.73) has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group PI^- with a = 5.8397(4), b = 9.8664(7), c = 14.1739(10) °A, α= 82.0150(10), β = 80.4540(10), γ= 82.3570(10)°, Z= 1, V= 792.47(10)°A^3, Dc = 2.112 g/cm^3,μ(MoKα) = 2.247 mm^-1, F(000) = 495, the final R = 0.0232 and wR = 0.0644 for 2748 observed reflections (I〉 2σ(I)). In the complex, seven-coordinated·Cd ions form a zigzag chain based on the alternated dinuclear Cd units. The neutral [Cu(pic)2(H2O)2] units are located at the centers of the inter space and fasten to the 1-D chain by hydrogen bonds.展开更多
Presented here is a new heterometallic Cu(I)-Sr(Ⅱ) coordination polymer, [Cu(3)Sr_2(isonic)_5 Br_2(H_2O)_3]n·n(H_2O)(1, Hisonic = isonicotinic acid), has been synthesized via the hydrothermal reactions of CuBr, ...Presented here is a new heterometallic Cu(I)-Sr(Ⅱ) coordination polymer, [Cu(3)Sr_2(isonic)_5 Br_2(H_2O)_3]n·n(H_2O)(1, Hisonic = isonicotinic acid), has been synthesized via the hydrothermal reactions of CuBr, Sr(NO_3)_2 and isonicotinic acid. The crystal structure is of triclinic system, space group P1 with a = 7.111(2), b = 14.934(4), c = 18.0255(11) ?, α = 83.137(15), β = 87.155(15), γ = 79.75(2)°, V = 1869.4(8) ?~3, C_(30)H_(29)Br_2Cu(3)N_5O_(14)Sr_2, Mr = 1209.27, Z = 2, Dc = 2.148 g/cm^3, F(000) = 1178, μ = 6.725 mm^(-1), R = 0.0500 and wR = 0.1008 for 4688 observed reflections(I > 2s(I)). Single-crystal X-ray diffraction analysis revealed that compound 1 features a 3 D heterometallic framework stabilized by bifunctional isonic ligands. In addition, the luminescent and photocatalytic properties of compound 1 were also investigated at room temperature.展开更多
Three two-dimensional(2-D) heterometallic chalcogenides [TM(tren)][InSbSe_3S](TM = Fe(1), Co(2), Mn(3); tren = tris(2-aminoethyl)-amine) have been solvothermally synthesized in this paper. Single-crystal X-ray analysi...Three two-dimensional(2-D) heterometallic chalcogenides [TM(tren)][InSbSe_3S](TM = Fe(1), Co(2), Mn(3); tren = tris(2-aminoethyl)-amine) have been solvothermally synthesized in this paper. Single-crystal X-ray analysis indicates that they are isostructural to each other except the different transition metal ions. These compounds contain an unsaturated complex cation [TM(tren)]^(2+), which can be further coordinated by the 2-D [InSbSSe_3]_n^(2n-) anion, resulting in a new neutral organic-decorated heterometallic chalcogenide. These compounds crystallize in monoclinic space group P21/c, with a = 11.768(12), b = 13.884(14), c = 11.095(11) ?, Z = 4, D_c =2.910 Mg·m^(-3), F(000) = 1304, M_r = 707.60 for 1; a = 11.843(9), b = 14.064(10), c = 10.979(8) ?, Z= 4, Dc = 2.875 Mg·m^(-3), F(000) = 1308, M_r = 710.68 for 2; a = 11.969(10), b = 14.191(11), c =11.112(9) ?, Z = 4, D_c = 2.779 Mg·m^(-3), F(000) = 1300, Mr = 706.69 for 3. The maximum and minimum peaks of compounds 1~3 are 6.996 and –2.880 e·?^(-3), 2.242 and –3.066 e·?^(-3), 3.655 and –3.569 e·?^(-3), respectively. These compounds were structurally characterized by powder X-ray diffraction measurement, thermal analysis, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy. A solid-state UV/Vis reflectance spectroscopy measurement on 1, 2 and 3 confirmed that these compounds are semiconductor materials.展开更多
A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occu...A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ(I).展开更多
A heterometallic metal-organic framework, Agln(nicotinate)4.1.5DMF, was obtained from the reaction of nicotinic acid, AgNO3 and In(NO3)3 in DMF. The complex was characterized by elemental analysis, infrared spectr...A heterometallic metal-organic framework, Agln(nicotinate)4.1.5DMF, was obtained from the reaction of nicotinic acid, AgNO3 and In(NO3)3 in DMF. The complex was characterized by elemental analysis, infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are: C28.5H26.5N55O9.5Agln, orthorhombic space group/222, a = 10.775(15), b = 11.939(18), c = 13.93(2) A, V= 1792(5) A3, Z = 2, Dc = 1.521 mg/m3,μ = 1.244 mm1, F(000) = 816, the final R = 0.0672 and wR= 0.1812 for 1912 observed reflections with I 〉 2σ(I). Single-crystal X-ray structure analysis reveals that nicotinate bridges In(III) and Ag(I) through carboxylate chelating with In(III) and pyridyl nitrogen atom coordinating to Ag(I), generating a new 2D network consisting of tetrahedral building units of [AgN4]+ and [In(COO)4]-.展开更多
A new tetranuclear square compound (H3O)[Sm2Co2(CDTA)2(DMF)2 (μ4-O) (H2O)6]ClO4 was synthesized through the assembly reaction of Co2+ , Sm3+ and trans-1,2-cclohexylenedinitrilotetraacetic acid (H4CDTA) ...A new tetranuclear square compound (H3O)[Sm2Co2(CDTA)2(DMF)2 (μ4-O) (H2O)6]ClO4 was synthesized through the assembly reaction of Co2+ , Sm3+ and trans-1,2-cclohexylenedinitrilotetraacetic acid (H4CDTA) in aqueous solution. X-ray crystal structural analysis shows that the compound belongs to the monoclinic C2/c space group, with a=27.213(2), b=10.5574(9), c=19.4923(17),β=98.799(1)°, V=5534.1(8)3 , C34H65ClCo2N6O30Sm2 , Mr=1491.93, Dc=1.791g/cm-3 , F(000)=2984,=2.820 mm-1 and Z=4. In the compound, Co2+ is 7-coordianted while Sm3+ is 9-coordinated. With the help of a central O2- and 8 carboxylate oxygen atoms, two Co2+ and two Sm3+ ions are linked into a square with the side length of 3.45 . Magnetic property was investigated.展开更多
Five novel SrⅡ-LnⅢ heterometallic coordination polymers based on pyridine-2,6- dicarboxylic acid (H2pda) and imidazole (im), namely, [LnSr(pda)3(H2O)5]-Him·C2H5OH·3H2O (Ln = Nd (1); Pr (2)), ...Five novel SrⅡ-LnⅢ heterometallic coordination polymers based on pyridine-2,6- dicarboxylic acid (H2pda) and imidazole (im), namely, [LnSr(pda)3(H2O)5]-Him·C2H5OH·3H2O (Ln = Nd (1); Pr (2)), [Ln2Sr(pda)6(H2O)5]-4Him·C2H5OH·5H2O (Ln = Nd (3); Pr (4)), and [ErSr(pda)3(H2O)4].Him-3.5H2O (5), have been prepared and structurally characterized. X-ray crystallographic analyses revealed that these complexes display three varieties of l-D chain structures. Several types of hydrogen bonding interactions are found for 1-5, which connect the 1 -D chain structures to form 2-D suoramolecular networks.展开更多
The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crysta...The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.展开更多
A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n(1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crys...A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n(1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a = 12.060(4), b = 8.493(3), c = 15.776(5)(A), β = 93.235(3)°, V = 1613.4(9) A3, Z = 4, Mr = 730.12, Dc = 3.006 Mg/m^3, μ = 6.581 mm-1, F(000) = 1368, the final R = 0.0283 and wR = 0.0866 for 2939 observed reflections with I 〉 2σ(I). Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.展开更多
Background and Originality Content The catalytic hydrosilylation of unsaturated hydrocarbons,facilitated by transition metal(TM),is widely recognized as a proficient technique for the synthesis of high-value organosil...Background and Originality Content The catalytic hydrosilylation of unsaturated hydrocarbons,facilitated by transition metal(TM),is widely recognized as a proficient technique for the synthesis of high-value organosilicon compounds'ti-4l over the past few decades,the most dominant cata.lysts in hydrosilylation processes have been constituted by pre-Ccious metar complexesroceinerecent vears omore sustainabile earth-abundant metal catalysts have received increased attentionj2-14l The classcal mechanism of transition metal-catalyzed hydrosilylation is generally accomplished through a series of fundamental processes(Scheme 1a),including(i)coordination and oxidative addition of Si-H bond to a low-valent metal center to form e.g.,o-complex or silyl metal hydride;(ii)insertion of.C-C multipe bonds intometal-hdridelsior metal-silicon bond;jiol and(ii)reductive elimination that forwards the hydrosilylated product with Markovnikov or anti-Markovnikov selectivity.展开更多
Extreme ultraviolet lithography(EUVL)and electron beam lithography(EBL)are considered to be crucial lithography techniques utilized in the fabrication of nanoscale semiconductor devices.However,the industry currently ...Extreme ultraviolet lithography(EUVL)and electron beam lithography(EBL)are considered to be crucial lithography techniques utilized in the fabrication of nanoscale semiconductor devices.However,the industry currently faces a scarcity of EUV photoresists that meet the increasingly challenging standards in terms of resolution,sensitivity and roughness.Metal oxo nanoclusters have garnered significant interest in the field of EUV photoresist due to their relatively stronger absorption cross-section for extreme ultraviolet light and lower dimensions.In this study,we utilize a heterometallic nanocluster strategy by a combination of titanium and zirconium metals to investigate their solubility,assess the suitability of various developers,and evaluate their performance in electron-beam and EUVL,as well as study their etch resistance for pattern transfer.We demonstrate that R-4 is able to get a critical dimension(CD)of 25 nm at low doses under EBL,as well as 50 nm resolution at EUVL with a remarkable sensitivity of 19.7 mJ cm−2.This study offers an efficient heterometallic method for optimizing the lithographic performance of metal oxo nanocluster photoresists,which can benefit the development of commercially viable next-generation EUV photoresists.展开更多
Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthe...Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthesized and structurally characterized.Single-crystal X-ray diffraction analyses reveal that the polyanions of La_(6)Co_(2)and La_(6)Mn_(2)consist of the uncommon 3d-4f-5d clusters{La_(6)W_(12)Co_(2)}and{La_(6)W_(12)Mn_(2)},which are encapsulated by four trilacunary Keggin tungstoantimonates to form the parallelogram-shaped title compounds.Additionally,the polyanions can be extended into a two-dimensional(2D)frame by the linkage of peripheral Na+ions.The inner space of the 2D layer was filled with water molecules and thus an H-bonded network was formed,which is expected to exhibit a fascinating proton conductivity.The study of water-assisted proton conduction demonstrated that La_(6)Co_(2)and La_(6)Mn_(2)were temperature-and humiditydependent proton conductors,respectively,and the proton conductivities could reach 1.3×10^(-2)and 2.3×10^(-2)S/cm at 65℃and 90%RH conditions.展开更多
Four novel compounds based on hexanuclear thorium cluster were synthesized and characterized.Compound 1[Th_(6)(HPy C)_(8)(HCOO)_(4)]is formed by replacing formate ligands of preassembled thorium cluster[Th_(6)O_(4)(OH...Four novel compounds based on hexanuclear thorium cluster were synthesized and characterized.Compound 1[Th_(6)(HPy C)_(8)(HCOO)_(4)]is formed by replacing formate ligands of preassembled thorium cluster[Th_(6)O_(4)(OH)_(4)(H_(2)O)_(6)(HCOO)_(12)]with eight H_(2)Py C(4-pyrazolecarboxylic acid)under solvothermal conditions.Each of the HPy C^(-)ligands is coordinated with one Cu^(2+)to form the(4,8)-connected scu-net structure of compound 2[(Cu Cl_(2))_(2)Th_(6)(HPy C)_8(HCOO)_(4)].In compound 3[(Cu Cl_(2))_(2)Th_(6)(HPy C)_(10)(HCOO)_(4)],ten of the formate ligands of preassembled Th_(6)cluster are replaced by HPy C^(-)ligands.Compared with compound 2,the two extra HPy C^(-)ligands in the equatorial plane of the Th_(6)cluster in compound 3 are not further connected to copper ions.Therefore,the topology structure of compound 3 is same with that of compound 2.Compound 4[(Cu_(3)Cl_(2))(Cu Cl_(2))Th_(6)(Py C)_(3)(HPy C)_(4)(HCOO)_(5)]contains three kinds of metal nodes,Th_(6)cluster,Cu_(3)cluster and mononuclear Cu^(2+),and exhibits a novel(5,7)-connected net structure,which was first discovered in actinide MOFs.Furthermore,considering the satisfactory stability of compound 4 and its unsaturated metal nodes and Lewis acid sites,the catalysis of cycloaddition of CO_(2)was further studied.We found that this thorium-copper heterometallic cluster organic framework can be used as a potential actinide functional material for catalyzing the efficient CO_(2)conversion to value-added products.展开更多
Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterize...Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterized.In these tetranuclear complexes,one polydentate L coordinates to one rare earth(Ⅲ)ion,and one cobalt(Ⅱ)ion,respectively,while two rare earth ions are bridged by four acetate groups.These complexes were applied in the copolymerization of cyclohexene oxide and CO_(2),which showed good activity(TON up to 440)and high poly(cyclohexene carbonate)selectivity(>99%).Kinetic studies determined the equation as rate=k[CHO]1[CO_(2)]0[initiator]1,which proves a first-order dependence on initiator concentrations and implies a synergistic mechanism with rare earth and cobalt ions cooperating in epoxide ring-opening and chain propagation.展开更多
Two unique two-dimensional(2D)Cd(Ⅱ)-Dy(Ⅲ)heterometallic coordination polymers,{[DyCd(HPMA)(PMA)_(2)(H_(2)O)_(4)]·2H_(2)O}_n(1)and[DyCd(PAA)(PMA)_(2)(H_(2)O)_(3)]_(n)(2,PAA^(-)=phenylacetate),were prepared succe...Two unique two-dimensional(2D)Cd(Ⅱ)-Dy(Ⅲ)heterometallic coordination polymers,{[DyCd(HPMA)(PMA)_(2)(H_(2)O)_(4)]·2H_(2)O}_n(1)and[DyCd(PAA)(PMA)_(2)(H_(2)O)_(3)]_(n)(2,PAA^(-)=phenylacetate),were prepared successfully based on the phenylmalonic acid(H_(2)PMA).The construction of two polymers is sensitive to the reaction temperature and can be synthesized directionally at room temperature and 90℃,respectively.Complexes 1 and 2 display 2D layer structures that include dinuclear[Dy_(2)]cluster node and Dy(Ⅲ)-based 1D zigzag chain motif severally.The Dy(Ⅲ)-based units in two structures both are spaced well with the adjacent ones by the diamagnetic Cd(Ⅱ)-based moieties.The magnetic studies reveal that 1 and 2both display slow magnetic relaxation with temperature-dependent relaxation peaks producing an effective energy barrier(Δτ)of 74.5 and 32.1 K,separately.Furthermore,the solid-state photophysical properties of 1 and 2 show strong characteristic luminescent emissions of Dy(Ⅲ)ion in the visible region.展开更多
A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphe...A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.展开更多
The layered heterometallic halide perovskites, as a newly explored material, have attracted great scientific attention. As one of the representatives of perovskite, lead-free or lead-substituted perovskite materials a...The layered heterometallic halide perovskites, as a newly explored material, have attracted great scientific attention. As one of the representatives of perovskite, lead-free or lead-substituted perovskite materials are widely applied in photovoltaic, sensors, catalysis, detectors and other fields. Therefore, it is urgent to carry out more systematic exploration and expand applicable preresearch, so as to make more interesting discoveries in this new hot spot. As an interesting candidate, heterometallic compounds will introduce more structural adjustability and novel physical properties, which is the main feature to be selected as the research hotspot. Here, we reported a lead-free bilayer heterometallic Ruddlesden-Popper(RP) type perovskite, [(MACH)_(2)CsAgBiBr_(7)](MACH = cyclohexanemethylamine), which possesses a reversible phase transition at 379.6 K/375.1 K during heating-cooling cycle. Besides, it exhibits reddish-brown light emission under 365 nm, meanwhile, CIE chromaticity coordinate is(0.32, 0.45) on the yellow side and correlated color temperature is about 6000 K. Moreover, both the experimental data and theoretical calculation results suggest that [(MACH)_(2)CsAgBiBr_(7)] shows indirect semiconducting characteristics. In summary, this work will inspire the design of lead-free heterometallic perovskite materials for the application of sensors and light-emitting diodes(LEDs) fields.展开更多
基金supported by the National Basic Research Program of China(973 Program,2012CB821702)the National Natural Science Foundation of China(21233009 and 21173221)the State Key Laboratory of Structural Chemistry
文摘Solvothermal reactions of Zn(NO3)2·6H20 with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional (3D) hereto-metallic inorganic-organic hybrid framework [ZnK2(m-BDC)ffH20)2]n (1, m-H2BDC = benzene-l,3-dicarboxylic acid). The crystal was characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction analysis. Complex 1 is of orthogonal crystal system, acentric space group Cmc2j with a = 19.764(6), b = 19.948(6), c = 12.039(4) A, V = 4746(3) A3, Z = 4, C32H20019KaZn2, Mr = 995.66, Dc= 1.393 g/cm3, F(000) = 2000 andp = 1.426 mm-1. The final R = 0.0761 and wR = 0.1841. The crystal exhibits remarkable blue luminescence emissions with high quantum yield of 56.02% and displays modest powder SHG efficiency of about 0.7 times that produced by a potassium dihydrogen phosphate (KDP) powder. In addition, it also exhibits potential ferroelectric property.
基金supported by the National Natural Science Foundation of China(No.20771083)
文摘Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13) and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.
基金supported by the National Natural Science Foundation of China (No. 20971004)the Key Project of Chinese Ministry of Education (No. 210102)
文摘A novel heterometallic complex,[Zn4Ni(OH)2(btec)2(titb)2(H2O)2]·2H2O(1)(H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trime-thylbenzene),has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817(10),b=11.878(11),c=14.569(14),α=71.762(12),β=76.122(13),γ=71.493(13)°,V=1665(3)3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F(000)=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections(Ⅰ 2σ(Ⅰ)).In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.
基金The work was supported by the National Natural Science Foundation of China (No. 50572024)
文摘A new heterometallic complex {[Cu(pic)2(H2O)2][Cd2(Hdipic)2(H2O)2Cl2]}n (Mr = 1007.73) has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group PI^- with a = 5.8397(4), b = 9.8664(7), c = 14.1739(10) °A, α= 82.0150(10), β = 80.4540(10), γ= 82.3570(10)°, Z= 1, V= 792.47(10)°A^3, Dc = 2.112 g/cm^3,μ(MoKα) = 2.247 mm^-1, F(000) = 495, the final R = 0.0232 and wR = 0.0644 for 2748 observed reflections (I〉 2σ(I)). In the complex, seven-coordinated·Cd ions form a zigzag chain based on the alternated dinuclear Cd units. The neutral [Cu(pic)2(H2O)2] units are located at the centers of the inter space and fasten to the 1-D chain by hydrogen bonds.
基金Supported by the grants from Guangdong University of Petrochemical Technology
文摘Presented here is a new heterometallic Cu(I)-Sr(Ⅱ) coordination polymer, [Cu(3)Sr_2(isonic)_5 Br_2(H_2O)_3]n·n(H_2O)(1, Hisonic = isonicotinic acid), has been synthesized via the hydrothermal reactions of CuBr, Sr(NO_3)_2 and isonicotinic acid. The crystal structure is of triclinic system, space group P1 with a = 7.111(2), b = 14.934(4), c = 18.0255(11) ?, α = 83.137(15), β = 87.155(15), γ = 79.75(2)°, V = 1869.4(8) ?~3, C_(30)H_(29)Br_2Cu(3)N_5O_(14)Sr_2, Mr = 1209.27, Z = 2, Dc = 2.148 g/cm^3, F(000) = 1178, μ = 6.725 mm^(-1), R = 0.0500 and wR = 0.1008 for 4688 observed reflections(I > 2s(I)). Single-crystal X-ray diffraction analysis revealed that compound 1 features a 3 D heterometallic framework stabilized by bifunctional isonic ligands. In addition, the luminescent and photocatalytic properties of compound 1 were also investigated at room temperature.
基金supported by the Natural Science Foundation of Inner Mongolia(No.2016MS0225)the Inner Mongolia Autonomous innovation guide project and Research Project of Higher School,Department of education of Inner Mongolia Autonomous Region(No.CXJJS17087)the National Natural Science Foundation of China(No.21461019)
文摘Three two-dimensional(2-D) heterometallic chalcogenides [TM(tren)][InSbSe_3S](TM = Fe(1), Co(2), Mn(3); tren = tris(2-aminoethyl)-amine) have been solvothermally synthesized in this paper. Single-crystal X-ray analysis indicates that they are isostructural to each other except the different transition metal ions. These compounds contain an unsaturated complex cation [TM(tren)]^(2+), which can be further coordinated by the 2-D [InSbSSe_3]_n^(2n-) anion, resulting in a new neutral organic-decorated heterometallic chalcogenide. These compounds crystallize in monoclinic space group P21/c, with a = 11.768(12), b = 13.884(14), c = 11.095(11) ?, Z = 4, D_c =2.910 Mg·m^(-3), F(000) = 1304, M_r = 707.60 for 1; a = 11.843(9), b = 14.064(10), c = 10.979(8) ?, Z= 4, Dc = 2.875 Mg·m^(-3), F(000) = 1308, M_r = 710.68 for 2; a = 11.969(10), b = 14.191(11), c =11.112(9) ?, Z = 4, D_c = 2.779 Mg·m^(-3), F(000) = 1300, Mr = 706.69 for 3. The maximum and minimum peaks of compounds 1~3 are 6.996 and –2.880 e·?^(-3), 2.242 and –3.066 e·?^(-3), 3.655 and –3.569 e·?^(-3), respectively. These compounds were structurally characterized by powder X-ray diffraction measurement, thermal analysis, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy. A solid-state UV/Vis reflectance spectroscopy measurement on 1, 2 and 3 confirmed that these compounds are semiconductor materials.
基金supported by the 973 Program (2007CB815301)the National Natural Science Foundation of China (21073192,20733003 and 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-H20)Fujian Province (2009HZ0006-1,2006L2005)
文摘A new tri-nuclear mixed metal thiolate complex [Ag(PPh3)2]2[Ni(edtO2)2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni(II) atom and the two silver(I) atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni(edt)2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581(11),b = 12.239(9),c = 22.316(17) ,β = 103.08(2)o,V = 3613(5) 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F(000) = 1604,T = 293(2) K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ(I).
基金supported by the National Natural Science Foundation of China(No.21401195)
文摘A heterometallic metal-organic framework, Agln(nicotinate)4.1.5DMF, was obtained from the reaction of nicotinic acid, AgNO3 and In(NO3)3 in DMF. The complex was characterized by elemental analysis, infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are: C28.5H26.5N55O9.5Agln, orthorhombic space group/222, a = 10.775(15), b = 11.939(18), c = 13.93(2) A, V= 1792(5) A3, Z = 2, Dc = 1.521 mg/m3,μ = 1.244 mm1, F(000) = 816, the final R = 0.0672 and wR= 0.1812 for 1912 observed reflections with I 〉 2σ(I). Single-crystal X-ray structure analysis reveals that nicotinate bridges In(III) and Ag(I) through carboxylate chelating with In(III) and pyridyl nitrogen atom coordinating to Ag(I), generating a new 2D network consisting of tetrahedral building units of [AgN4]+ and [In(COO)4]-.
基金Supported by the NNSFC (21071025, 91122031)Doctoral Fund of Ministry of Education of China (20100041120021)DUT (893127 and 851004)
文摘A new tetranuclear square compound (H3O)[Sm2Co2(CDTA)2(DMF)2 (μ4-O) (H2O)6]ClO4 was synthesized through the assembly reaction of Co2+ , Sm3+ and trans-1,2-cclohexylenedinitrilotetraacetic acid (H4CDTA) in aqueous solution. X-ray crystal structural analysis shows that the compound belongs to the monoclinic C2/c space group, with a=27.213(2), b=10.5574(9), c=19.4923(17),β=98.799(1)°, V=5534.1(8)3 , C34H65ClCo2N6O30Sm2 , Mr=1491.93, Dc=1.791g/cm-3 , F(000)=2984,=2.820 mm-1 and Z=4. In the compound, Co2+ is 7-coordianted while Sm3+ is 9-coordinated. With the help of a central O2- and 8 carboxylate oxygen atoms, two Co2+ and two Sm3+ ions are linked into a square with the side length of 3.45 . Magnetic property was investigated.
基金Supported by Hundreds of Talents Program(2005012)of CASNNSFC(21272167 and 21201127)Priority Academic Program Development of Jiangsu Higher Education Institution and Graduate Education Innovation Project in Jiangsu Province(CXZZ12_0808)
文摘Five novel SrⅡ-LnⅢ heterometallic coordination polymers based on pyridine-2,6- dicarboxylic acid (H2pda) and imidazole (im), namely, [LnSr(pda)3(H2O)5]-Him·C2H5OH·3H2O (Ln = Nd (1); Pr (2)), [Ln2Sr(pda)6(H2O)5]-4Him·C2H5OH·5H2O (Ln = Nd (3); Pr (4)), and [ErSr(pda)3(H2O)4].Him-3.5H2O (5), have been prepared and structurally characterized. X-ray crystallographic analyses revealed that these complexes display three varieties of l-D chain structures. Several types of hydrogen bonding interactions are found for 1-5, which connect the 1 -D chain structures to form 2-D suoramolecular networks.
基金Nanjing University of Posts and Telecommunications (No. NY209032)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education,Science Foundation for Youths of Guangxi Province (No. 0991089)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.
基金supported by the National Natural Science of Foundation of China(No.31270388)
文摘A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n(1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a = 12.060(4), b = 8.493(3), c = 15.776(5)(A), β = 93.235(3)°, V = 1613.4(9) A3, Z = 4, Mr = 730.12, Dc = 3.006 Mg/m^3, μ = 6.581 mm-1, F(000) = 1368, the final R = 0.0283 and wR = 0.0866 for 2939 observed reflections with I 〉 2σ(I). Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.
基金supported by the National Natural Science Foundation of China(22371198)the Postdoctoral Fellowship Programof CPSF(GZC20231885).
文摘Background and Originality Content The catalytic hydrosilylation of unsaturated hydrocarbons,facilitated by transition metal(TM),is widely recognized as a proficient technique for the synthesis of high-value organosilicon compounds'ti-4l over the past few decades,the most dominant cata.lysts in hydrosilylation processes have been constituted by pre-Ccious metar complexesroceinerecent vears omore sustainabile earth-abundant metal catalysts have received increased attentionj2-14l The classcal mechanism of transition metal-catalyzed hydrosilylation is generally accomplished through a series of fundamental processes(Scheme 1a),including(i)coordination and oxidative addition of Si-H bond to a low-valent metal center to form e.g.,o-complex or silyl metal hydride;(ii)insertion of.C-C multipe bonds intometal-hdridelsior metal-silicon bond;jiol and(ii)reductive elimination that forwards the hydrosilylated product with Markovnikov or anti-Markovnikov selectivity.
基金supported by the National Natural Science Foundation of China(22271284 and 91961108)“the Fundamental Research Funds for the Central Universities”,Nankai University(075-63233091)。
文摘Extreme ultraviolet lithography(EUVL)and electron beam lithography(EBL)are considered to be crucial lithography techniques utilized in the fabrication of nanoscale semiconductor devices.However,the industry currently faces a scarcity of EUV photoresists that meet the increasingly challenging standards in terms of resolution,sensitivity and roughness.Metal oxo nanoclusters have garnered significant interest in the field of EUV photoresist due to their relatively stronger absorption cross-section for extreme ultraviolet light and lower dimensions.In this study,we utilize a heterometallic nanocluster strategy by a combination of titanium and zirconium metals to investigate their solubility,assess the suitability of various developers,and evaluate their performance in electron-beam and EUVL,as well as study their etch resistance for pattern transfer.We demonstrate that R-4 is able to get a critical dimension(CD)of 25 nm at low doses under EBL,as well as 50 nm resolution at EUVL with a remarkable sensitivity of 19.7 mJ cm−2.This study offers an efficient heterometallic method for optimizing the lithographic performance of metal oxo nanocluster photoresists,which can benefit the development of commercially viable next-generation EUV photoresists.
基金supported by the National Natural Science Foundation of China(No.22071045)the Excellent Youth Science Fund Project of Henan Province(No.202300410042)+2 种基金the Natural Science Foundation of Henan Province(No.232300420372)Henan Universitythe State Key Laboratory of Physical Chemistry of the Solid Surface of Xiamen University。
文摘Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthesized and structurally characterized.Single-crystal X-ray diffraction analyses reveal that the polyanions of La_(6)Co_(2)and La_(6)Mn_(2)consist of the uncommon 3d-4f-5d clusters{La_(6)W_(12)Co_(2)}and{La_(6)W_(12)Mn_(2)},which are encapsulated by four trilacunary Keggin tungstoantimonates to form the parallelogram-shaped title compounds.Additionally,the polyanions can be extended into a two-dimensional(2D)frame by the linkage of peripheral Na+ions.The inner space of the 2D layer was filled with water molecules and thus an H-bonded network was formed,which is expected to exhibit a fascinating proton conductivity.The study of water-assisted proton conduction demonstrated that La_(6)Co_(2)and La_(6)Mn_(2)were temperature-and humiditydependent proton conductors,respectively,and the proton conductivities could reach 1.3×10^(-2)and 2.3×10^(-2)S/cm at 65℃and 90%RH conditions.
基金support of the National Natural Science Foundation of China(Nos.22076187,22122609)the Hunan Province Natural Science Foundation of China(No.2023JJ40530)+1 种基金the Scientific Research Fund of Hunan Provincial Education Department(No.22C0202)The National Science Fund for Distinguished Young Scholars(No.21925603)。
文摘Four novel compounds based on hexanuclear thorium cluster were synthesized and characterized.Compound 1[Th_(6)(HPy C)_(8)(HCOO)_(4)]is formed by replacing formate ligands of preassembled thorium cluster[Th_(6)O_(4)(OH)_(4)(H_(2)O)_(6)(HCOO)_(12)]with eight H_(2)Py C(4-pyrazolecarboxylic acid)under solvothermal conditions.Each of the HPy C^(-)ligands is coordinated with one Cu^(2+)to form the(4,8)-connected scu-net structure of compound 2[(Cu Cl_(2))_(2)Th_(6)(HPy C)_8(HCOO)_(4)].In compound 3[(Cu Cl_(2))_(2)Th_(6)(HPy C)_(10)(HCOO)_(4)],ten of the formate ligands of preassembled Th_(6)cluster are replaced by HPy C^(-)ligands.Compared with compound 2,the two extra HPy C^(-)ligands in the equatorial plane of the Th_(6)cluster in compound 3 are not further connected to copper ions.Therefore,the topology structure of compound 3 is same with that of compound 2.Compound 4[(Cu_(3)Cl_(2))(Cu Cl_(2))Th_(6)(Py C)_(3)(HPy C)_(4)(HCOO)_(5)]contains three kinds of metal nodes,Th_(6)cluster,Cu_(3)cluster and mononuclear Cu^(2+),and exhibits a novel(5,7)-connected net structure,which was first discovered in actinide MOFs.Furthermore,considering the satisfactory stability of compound 4 and its unsaturated metal nodes and Lewis acid sites,the catalysis of cycloaddition of CO_(2)was further studied.We found that this thorium-copper heterometallic cluster organic framework can be used as a potential actinide functional material for catalyzing the efficient CO_(2)conversion to value-added products.
基金financial support from the National Natural Science Foundation of China(21871198)the Major Research Project of the Natural Science of the Jiangsu Higher Education Institutions(19KJA360005 and 19KJA320007),and PAPD.
文摘Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterized.In these tetranuclear complexes,one polydentate L coordinates to one rare earth(Ⅲ)ion,and one cobalt(Ⅱ)ion,respectively,while two rare earth ions are bridged by four acetate groups.These complexes were applied in the copolymerization of cyclohexene oxide and CO_(2),which showed good activity(TON up to 440)and high poly(cyclohexene carbonate)selectivity(>99%).Kinetic studies determined the equation as rate=k[CHO]1[CO_(2)]0[initiator]1,which proves a first-order dependence on initiator concentrations and implies a synergistic mechanism with rare earth and cobalt ions cooperating in epoxide ring-opening and chain propagation.
基金Project supported by the National Natural Science Foundation of China(21901152)Natural Science Foundation of Henan Province(222300420509)。
文摘Two unique two-dimensional(2D)Cd(Ⅱ)-Dy(Ⅲ)heterometallic coordination polymers,{[DyCd(HPMA)(PMA)_(2)(H_(2)O)_(4)]·2H_(2)O}_n(1)and[DyCd(PAA)(PMA)_(2)(H_(2)O)_(3)]_(n)(2,PAA^(-)=phenylacetate),were prepared successfully based on the phenylmalonic acid(H_(2)PMA).The construction of two polymers is sensitive to the reaction temperature and can be synthesized directionally at room temperature and 90℃,respectively.Complexes 1 and 2 display 2D layer structures that include dinuclear[Dy_(2)]cluster node and Dy(Ⅲ)-based 1D zigzag chain motif severally.The Dy(Ⅲ)-based units in two structures both are spaced well with the adjacent ones by the diamagnetic Cd(Ⅱ)-based moieties.The magnetic studies reveal that 1 and 2both display slow magnetic relaxation with temperature-dependent relaxation peaks producing an effective energy barrier(Δτ)of 74.5 and 32.1 K,separately.Furthermore,the solid-state photophysical properties of 1 and 2 show strong characteristic luminescent emissions of Dy(Ⅲ)ion in the visible region.
基金supported by National Natural Science Foundation of China(grant nos.21871141,21871142,22071109,21901122,22225109,22171139).
文摘A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.
基金supported by the National Natural Science Foundation of China (No. 21991141)Zhejiang Normal University。
文摘The layered heterometallic halide perovskites, as a newly explored material, have attracted great scientific attention. As one of the representatives of perovskite, lead-free or lead-substituted perovskite materials are widely applied in photovoltaic, sensors, catalysis, detectors and other fields. Therefore, it is urgent to carry out more systematic exploration and expand applicable preresearch, so as to make more interesting discoveries in this new hot spot. As an interesting candidate, heterometallic compounds will introduce more structural adjustability and novel physical properties, which is the main feature to be selected as the research hotspot. Here, we reported a lead-free bilayer heterometallic Ruddlesden-Popper(RP) type perovskite, [(MACH)_(2)CsAgBiBr_(7)](MACH = cyclohexanemethylamine), which possesses a reversible phase transition at 379.6 K/375.1 K during heating-cooling cycle. Besides, it exhibits reddish-brown light emission under 365 nm, meanwhile, CIE chromaticity coordinate is(0.32, 0.45) on the yellow side and correlated color temperature is about 6000 K. Moreover, both the experimental data and theoretical calculation results suggest that [(MACH)_(2)CsAgBiBr_(7)] shows indirect semiconducting characteristics. In summary, this work will inspire the design of lead-free heterometallic perovskite materials for the application of sensors and light-emitting diodes(LEDs) fields.