For the further improvement of the power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs),the buried interface between the perovskite and the electron transport layer is crucial.However,it is ch...For the further improvement of the power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs),the buried interface between the perovskite and the electron transport layer is crucial.However,it is challenging to effectively optimize this interface as it is buried beneath the perovskite film.Herein,we have designed and synthesized a series of multifunctional organic-inorganic(OI)complexes as buried interfacial material to promote electron extraction,as well as the crystal growth of the perovskite.The OI complex with BF4−group not only eliminates oxygen vacancies on the SnO_(2) surface but also balances energy level alignment between SnO_(2) and perovskite,providing a favorable environment for charge carrier extraction.Moreover,OI complex with amine(−NH_(2))functional group can regulate the crystallization of the perovskite film via interaction with PbI2,resulting in highly crystallized perovskite film with large grains and low defect density.Consequently,with rational molecular design,the PSCs with optimal OI complex buried interface layer which contains both BF4−and−NH_(2) functional groups yield a champion device efficiency of 23.69%.More importantly,the resulting unencapsulated device performs excellent ambient stability,maintaining over 90%of its initial efficiency after 2000 h storage,and excellent light stability of 91.5%remaining PCE in the maximum power point tracking measurement(under continuous 100 mW cm−2 light illumination in N2 atmosphere)after 500 h.展开更多
A novel organic-inorganic complex [Ca(DMSO)5(H2O)]2SiMo12O40 was synthesized from CaCl2, DMSO and H4SiMo12O40nH2O in mixed solvent of acetonitrile and water. Its structure was characterized with elemental analysis, I...A novel organic-inorganic complex [Ca(DMSO)5(H2O)]2SiMo12O40 was synthesized from CaCl2, DMSO and H4SiMo12O40nH2O in mixed solvent of acetonitrile and water. Its structure was characterized with elemental analysis, IR and X-ray diffraction analysis.展开更多
The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)212[SiMo12O40].2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using...The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)212[SiMo12O40].2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper(I/) centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.展开更多
An organic-inorganic mercury coordination compound [Hg(DMSO)2(H2O)]2 [GeW12O40]· DMSO·H2O (DMSO =dimethyl sulfoxide) has been synthesized and characterized by IR, UV spectra, elemental analysis, TG-DTA...An organic-inorganic mercury coordination compound [Hg(DMSO)2(H2O)]2 [GeW12O40]· DMSO·H2O (DMSO =dimethyl sulfoxide) has been synthesized and characterized by IR, UV spectra, elemental analysis, TG-DTA and X-ray single-crystal diffraction. Structural analysis revealed that in the title compound, the mercury is three-coordinated to show the distorted trigonal cone geometry, and depending on the electrostatic interaction to connect the polyanion [α-GeW12O40]^4-. TG-DTA study manifests the decomposition temperature of the polyanion framework in the title compound is 513.5℃, which is much higher than that of the anion framework. It means that the formation of the organic-inorganic mercury coordination compound made the polyanion [α-GeW12O40]^4- to he more stable.展开更多
A novel inorganic-organic hybrid based on isopolyanion,{[Cu2(phen)2(μ-ox)][H2Mo8O26]}·4EtOH·Et2O(1) (phen=phenanthroline,ox=oxalate),was synthesized under open-air mild reaction conditions,and chara...A novel inorganic-organic hybrid based on isopolyanion,{[Cu2(phen)2(μ-ox)][H2Mo8O26]}·4EtOH·Et2O(1) (phen=phenanthroline,ox=oxalate),was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters:a=1.1075(5) nm,b=1.1608(5) nm,c=1.3333(5) nm,α=91.683(5)o,β=113.996(5)o,γ=112.170(5)o,V=1.4159(10) nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F(000)=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-(Mo8O26)4-] and oxalato-bridged dinuclear copper complex cations [Cu2(phen)2(μ-ox)]2+.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment (CCDC No.665101).展开更多
A novel organic-inorganic hybrid compound {[Cu(2,2'-bpy)_2]_2Mo_8O_(26)} hasbeen hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.The compound crystallizes in the ortho...A novel organic-inorganic hybrid compound {[Cu(2,2'-bpy)_2]_2Mo_8O_(26)} hasbeen hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.The compound crystallizes in the orthorhombic space group, Pna2_1, with a = 2.4164(5), b =1.8281(4), c = 1.1877(2) nm, V = 5.247(2) nm^3, Z = 4, and final R_1 = 0.0331, wR_2 = 0.0727. Thestructure consists of discrete {[Cu(2,2'-bpy)_2]_2Mo_8O_(26)} clusters, constructed from aβ-octamolybdate subunit [Mo_8O_(26)]^(4-) covalently bonded to two [Cu(2,2'-bpy)_2]^(2+)coordination complex cations via bridging oxo groups. In addition, the spectroscopic properties andthermal behavior of this compound have been investigated by spectroscopic techniques (UV-vis, IR,Raman and EPR spectra) and TG analysis.展开更多
A new copper(II)-2,2'-biimidazole metal-organic POMs-supported compound [Cu(H2biim)2]{[Cu(H2biim)212[H10W12O44]}'8H2O (H2biim = 2,2'-biimidazole) has been success- fully synthesized under hydrothermal condi...A new copper(II)-2,2'-biimidazole metal-organic POMs-supported compound [Cu(H2biim)2]{[Cu(H2biim)212[H10W12O44]}'8H2O (H2biim = 2,2'-biimidazole) has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800(2), b = 13.437(3), c = 13.685(3) A, V = 1922.5(7) A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F(000) = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections (I 〉 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu(H2biim)2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.'-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.展开更多
[Co^11(phen)3]2[{(ZnW12O40)Co^11(phen)2(H2O)}2Co^11(trien)2(NaH2O)2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable t...[Co^11(phen)3]2[{(ZnW12O40)Co^11(phen)2(H2O)}2Co^11(trien)2(NaH2O)2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{(ZnW12O40)Co(phen)2(H2O)}2Co(C6H18N4)2·(NaH2O)2]^4- in which each supported Keggin anion [(ZnW12O40Co^11(phen)2(H2O)]^4- acts as a ligand to coordinate to central bridging Co^2+ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction(0=-46.796 K).展开更多
Two d10 metal-organic complexes, [ZnBr2(DICNQ)2] (1) and [AgCN(DICNQ)]2(2), were prepared from ZnBr2 and AgCN with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reactions, respectively, and characte...Two d10 metal-organic complexes, [ZnBr2(DICNQ)2] (1) and [AgCN(DICNQ)]2(2), were prepared from ZnBr2 and AgCN with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reactions, respectively, and characterized by single-crystal X-ray diffraction analyses, IR spectroscopy, and photoluminescent measurement. Compound 1 crystallizes in monoclinic, space group C2/c with a=8.436(2), b=13.011(3), c=27.565(6),β=97.90(3) , V=2997.0(1)3 , Z=4, Mr=789.73, Dc=1.750 g/cm3 ,μ=3.533 mm-1 , F(000)=1552, S=1.007 and T=293(2) K. The final R=0.0739 and wR=0.1380 for 1561 observed reflections with I 〉 2σ(I). Compound 2 crystallizes in monoclinic, space group P21/c with a=24.202(6), b=7.1619(17), c=18.339(5),β=111.8380(10) , V=2950.6(1)3 , Z=4, Mr=832.32, Dc=1.874 g/cm 3 ,μ=1.382 mm-1 , F(000)=1632, S=1.002 and T=293(2) K. The final R=0.0389 and wR=0.1257 for 4812 observed reflections with I 〉 2σ(I). Both compounds form packing structures by π…π stacking interactions and C-H…N or C-H…Br hydrogen-bonding interactions. Compounds 1 and 2 show similar photoluminescent spectra with emission maxima at ca. 430 nm in diluted acetonitrile solution (1×10-5 mol L-1 ) at room temperature.展开更多
基金The authors acknowledge the financial support from the Natural Science Foundation of China(Nos.21931002 and 22101123)the National Key Research and Development Program of China(2018YFB0704100)+4 种基金the Shenzhen Science and Technology Innovation Committee(no.JCYJ20200109140812302)the Leading talents of Guangdong province program(2016LJ06N507)the Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(no.2018B030322001)the Guangdong Provincial Key Laboratory of Catalysis(no.2020B121201002)Outstanding Talents Training Fund in Shenzhen.
文摘For the further improvement of the power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs),the buried interface between the perovskite and the electron transport layer is crucial.However,it is challenging to effectively optimize this interface as it is buried beneath the perovskite film.Herein,we have designed and synthesized a series of multifunctional organic-inorganic(OI)complexes as buried interfacial material to promote electron extraction,as well as the crystal growth of the perovskite.The OI complex with BF4−group not only eliminates oxygen vacancies on the SnO_(2) surface but also balances energy level alignment between SnO_(2) and perovskite,providing a favorable environment for charge carrier extraction.Moreover,OI complex with amine(−NH_(2))functional group can regulate the crystallization of the perovskite film via interaction with PbI2,resulting in highly crystallized perovskite film with large grains and low defect density.Consequently,with rational molecular design,the PSCs with optimal OI complex buried interface layer which contains both BF4−and−NH_(2) functional groups yield a champion device efficiency of 23.69%.More importantly,the resulting unencapsulated device performs excellent ambient stability,maintaining over 90%of its initial efficiency after 2000 h storage,and excellent light stability of 91.5%remaining PCE in the maximum power point tracking measurement(under continuous 100 mW cm−2 light illumination in N2 atmosphere)after 500 h.
文摘A novel organic-inorganic complex [Ca(DMSO)5(H2O)]2SiMo12O40 was synthesized from CaCl2, DMSO and H4SiMo12O40nH2O in mixed solvent of acetonitrile and water. Its structure was characterized with elemental analysis, IR and X-ray diffraction analysis.
基金financially supported by the National Natural Science Foundation of China (No. 2057023)the Program for New Century Excellent Talents in Universities of Henan Province (No. 2005HANCET)+2 种基金the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20040475001)Henan Innovation Project for University Prominent Re-search Talents (No. 2005KYCX011)the Natural Science Foundation of Henan Province, China (No. 0411051700)
文摘The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)212[SiMo12O40].2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper(I/) centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.
文摘An organic-inorganic mercury coordination compound [Hg(DMSO)2(H2O)]2 [GeW12O40]· DMSO·H2O (DMSO =dimethyl sulfoxide) has been synthesized and characterized by IR, UV spectra, elemental analysis, TG-DTA and X-ray single-crystal diffraction. Structural analysis revealed that in the title compound, the mercury is three-coordinated to show the distorted trigonal cone geometry, and depending on the electrostatic interaction to connect the polyanion [α-GeW12O40]^4-. TG-DTA study manifests the decomposition temperature of the polyanion framework in the title compound is 513.5℃, which is much higher than that of the anion framework. It means that the formation of the organic-inorganic mercury coordination compound made the polyanion [α-GeW12O40]^4- to he more stable.
基金Supported by the National Natural Science Foundation of China(No.20871022)Natural Science Foundation of Liaoning Province,China(No.20061073)
文摘A novel inorganic-organic hybrid based on isopolyanion,{[Cu2(phen)2(μ-ox)][H2Mo8O26]}·4EtOH·Et2O(1) (phen=phenanthroline,ox=oxalate),was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters:a=1.1075(5) nm,b=1.1608(5) nm,c=1.3333(5) nm,α=91.683(5)o,β=113.996(5)o,γ=112.170(5)o,V=1.4159(10) nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F(000)=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-(Mo8O26)4-] and oxalato-bridged dinuclear copper complex cations [Cu2(phen)2(μ-ox)]2+.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment (CCDC No.665101).
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 710 0 7)andtheFoundationforUniversityKeyTeacherbytheMinistryofEducationofChina
文摘A novel organic-inorganic hybrid compound {[Cu(2,2'-bpy)_2]_2Mo_8O_(26)} hasbeen hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.The compound crystallizes in the orthorhombic space group, Pna2_1, with a = 2.4164(5), b =1.8281(4), c = 1.1877(2) nm, V = 5.247(2) nm^3, Z = 4, and final R_1 = 0.0331, wR_2 = 0.0727. Thestructure consists of discrete {[Cu(2,2'-bpy)_2]_2Mo_8O_(26)} clusters, constructed from aβ-octamolybdate subunit [Mo_8O_(26)]^(4-) covalently bonded to two [Cu(2,2'-bpy)_2]^(2+)coordination complex cations via bridging oxo groups. In addition, the spectroscopic properties andthermal behavior of this compound have been investigated by spectroscopic techniques (UV-vis, IR,Raman and EPR spectra) and TG analysis.
基金supported by the Knowledge Innovation Program(No.KJCX2-EW-H01)of Chinese Academy of SciencesNational Natural Science Foundation of China(No.21003125,21073190)Natural Science Foundation of Fujian Province(2010J05040,2010J01057)
文摘A new copper(II)-2,2'-biimidazole metal-organic POMs-supported compound [Cu(H2biim)2]{[Cu(H2biim)212[H10W12O44]}'8H2O (H2biim = 2,2'-biimidazole) has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800(2), b = 13.437(3), c = 13.685(3) A, V = 1922.5(7) A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F(000) = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections (I 〉 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu(H2biim)2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.'-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.
基金Supported by the National Natural Science Foundation of China(No.33970842) the Analysis and Testing Foundation of Northeast Normal University, China
文摘[Co^11(phen)3]2[{(ZnW12O40)Co^11(phen)2(H2O)}2Co^11(trien)2(NaH2O)2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{(ZnW12O40)Co(phen)2(H2O)}2Co(C6H18N4)2·(NaH2O)2]^4- in which each supported Keggin anion [(ZnW12O40Co^11(phen)2(H2O)]^4- acts as a ligand to coordinate to central bridging Co^2+ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction(0=-46.796 K).
基金Supported by the NNSFC (90922013,21003126)Key Project from the CAS (KJCX2-EW-H03)the NSF of Fujian Province (2010H0022,2011J06006)
文摘Two d10 metal-organic complexes, [ZnBr2(DICNQ)2] (1) and [AgCN(DICNQ)]2(2), were prepared from ZnBr2 and AgCN with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reactions, respectively, and characterized by single-crystal X-ray diffraction analyses, IR spectroscopy, and photoluminescent measurement. Compound 1 crystallizes in monoclinic, space group C2/c with a=8.436(2), b=13.011(3), c=27.565(6),β=97.90(3) , V=2997.0(1)3 , Z=4, Mr=789.73, Dc=1.750 g/cm3 ,μ=3.533 mm-1 , F(000)=1552, S=1.007 and T=293(2) K. The final R=0.0739 and wR=0.1380 for 1561 observed reflections with I 〉 2σ(I). Compound 2 crystallizes in monoclinic, space group P21/c with a=24.202(6), b=7.1619(17), c=18.339(5),β=111.8380(10) , V=2950.6(1)3 , Z=4, Mr=832.32, Dc=1.874 g/cm 3 ,μ=1.382 mm-1 , F(000)=1632, S=1.002 and T=293(2) K. The final R=0.0389 and wR=0.1257 for 4812 observed reflections with I 〉 2σ(I). Both compounds form packing structures by π…π stacking interactions and C-H…N or C-H…Br hydrogen-bonding interactions. Compounds 1 and 2 show similar photoluminescent spectra with emission maxima at ca. 430 nm in diluted acetonitrile solution (1×10-5 mol L-1 ) at room temperature.