CN103641851B - Organic hybrid Pb-Ag hybrid metal iodide of a kind of coordination function and preparation method thereof - Google Patents

Organic hybrid Pb-Ag hybrid metal iodide of a kind of coordination function and preparation method thereof Download PDF

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CN103641851B
CN103641851B CN201310593995.2A CN201310593995A CN103641851B CN 103641851 B CN103641851 B CN 103641851B CN 201310593995 A CN201310593995 A CN 201310593995A CN 103641851 B CN103641851 B CN 103641851B
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iodide
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贾定先
沈亚利
陆加林
陈瑞红
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Suzhou University
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Abstract

The invention discloses a kind of organic hybrid Pb-Ag hybrid metal iodide of coordination function, it is characterized in that: the general formula of these iodide is [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] n, wherein: L is the one in following ethylene polyamine part, and L and m meets following condition: when L is a kind of in quadrol, 1,2-propylene diamine and 1,3-propylene diamine, m=2; When L is a kind of in N, N, N ˊ, N ˊ-Tetramethyl Ethylene Diamine, triethylene tetramine and tetraethylene pentamine, m=1.The present invention, by the chelating ligands effect of organic constituent and metal, makes Pb-Ag hybrid metal iodide have different structures and photoelectric property, thus greatly improves the thermostability of iodide, obtain the controlled organic hybrid semiconductor material of energy gap with this.The present invention provides the preparation method of described hybrid metal iodide simultaneously, and it is by single step reaction synthesis hybrid metal iodide, and it is convenient that synthesis is simple, reaction raw materials is easy to get, product separation is purified, and yield is high, and product structure is clear and definite.

Description

Organic hybrid Pb-Ag hybrid metal iodide of a kind of coordination function and preparation method thereof
Technical field
Organic hybrid Pb-Ag hybrid metal iodide that the present invention relates to a kind of coordination function and preparation method thereof.
Background technology
The iodo plumbite of organic hybrid and iodo silver hydrochlorate are the semiconductor material of excellent property, photoelectric material and temperature change material, and its physico-chemical property such as optical, electrical and hot is subject to impact and the control of its organic constituent, therefore has broad application prospects in Inorganic-Organic Hybrid Material and matrix material etc.Iodo plumbite and iodo silver hydrochlorate structural unit are respectively PbI 6octahedron and AgI 4tetrahedron, under the effect of the structure directing agents such as organic cation, PbI 6or AgI 4structural unit is by top, altogether limit or coplanar mode carry out self-assembly, [the Pb of formation various structures respectively altogether xi y] z–[Ag xi y] z–binary Aggregation ion, their polymerization methods is relevant with kind with organic cations structure with the polymerization degree, therefore can affect iodo plumbite and the sour structures and characteristics of iodo silver by structure directing agents such as organic cations.But, because organic constituent and plumbous iodine, silver-colored iodine inorganic component interact with very weak intermolecular forces, when the metal iodide of this traditional organic hybrid is heated, usually decompose because losing organic constituent in 80 –, 150 DEG C of temperature ranges, the thermostability that the iodo hydrochlorate of this organic hybrid is lower greatly limit its range of application.
On the other hand, I – ion and Pb 2+and A g +ion all has stronger coordination ability, and has multipair lone-pair electron, can with μ-I, μ 3-I and μ 4bridging coordination mode and the Pb such as-I 2+and Ag +ion coordination.Therefore, by the bridging effect of I – ion, PbI 6and AgI 4structural unit can be polymerized jointly, thus forms the more complicated [Pb of structure xag yi z] n–ternary iodo-acid salt ion.Between Pb – Ag metal and metal function and Pb – I and Ag – I polar link synergy under, make this kind of ternary compound have more abundant photoelectric property.At present, people compare deep research in organic hybrid iodo plumbite and organic hybrid iodo silver hydrochlorate, have synthesized the plumbous iodine of a series of this kind of binary and silver-colored iodide, but, to containing PbI 6and AgI 4the research of the Pb-Ag Ternary Iodide of the coordination organic hybrid of mixed structure unit has no report.
Report about the iodo plumbite of organic hybrid: have many bibliographical informations containing organic cations iodo plumbite, representative research has:
(1) 2004 year and 2007, the people such as N.Mercier were with the organic amine OH (CH containing hydroxyl 2) 2nH 2with halo organic amine X-(CH 2) 2nH 2(X=Cl, Br) is structure directing agent, has synthesized [HO (the CH with two-dimentional perovskite typed laminate structure respectively 2) 2nH 3] 2pbI 4[X (CH 2) 2nH 3] 2pbI 4.[HO (CH 2) 2nH 3] 2pbI 4for temperature change material, undergo phase transition 96 DEG C time, become orthorhombic crystal phase mutually from oblique crystal, this phase transformation is reversible, by there is O – HI in compound and N – HI hydrogen bond action causes simultaneously.[X (CH 2) 2nH 3] 2pbI 4for excellent semiconductor material, its energy gap is 2.2eV(see N.Mercier, S.Poiroux, A.RiouandP.Batail, Inorg.Chem., 2004,43,8361 – 8366; S.Sourisseau, N.Louvain, W.Bi, N.Mercier, D.Rondeau, F.Boucher, J.-Y.Buzar é andC.Legein, Chem.Mater., 2007,19,600-607);
(2) 2007 years, the people such as N.Mercier were with NH 2(CH 2) 2sS (CH 2) 2nH 2for structure directing agent, synthesize the iodo plumbite [NH containing protonated organic amine cation respectively 3(CH 2) 2sS (CH 2) 2nH 3] 4pb 3i 14i 2, [NH 3(CH 2) 2sS (CH 2) 2nH 3] 6pb 5i 224H 2o and [NH 3(CH 2) 2sS (CH 2) 2nH 3] 6pb 5i 222H 2o, three compounds are two-dimentional perovskite typed laminate structure, in the temperature range of 37-87 DEG C, show ionic conductivity, and the specific conductivity 57 DEG C time is 6 × 10 -7scm -1.(see: N.Louvain, W.Bi, N.Mercier, J.-Y.Buzar é, C.LegeinandG.Corbel, DaltonTrans., 2007,965 – 970);
(3) 2008 years, the people such as G.C.Guo synthesized the organic compound with three-dimensional structure (EDAMP) first with solvent thermal process 2n(Pb 7i 18) n4nH 2o (EDAMP=Et 2nHC 6h 4-CH 2c 6h 4nHEt 2), this compound has photochromic properties, and be the radiation of visible light of 550nm through wavelength, compound becomes light green from yellow, and after the rayed that wavelength is 300nm, becomes deep green again.(see: Z.J.Zhang, S.C.Xiang, G.C.Guo, G.Xu, M.S.Wang, J.P.Zou, S.P.GuoandJ.S.Huang, Angew.Chem.Int.Ed., 2008,47,4149 – 4152);
Report about the iodo silver hydrochlorate of organic hybrid:
(1) 1999 year, the people such as G.C.Papavassiliou were with quaternary ammonium salt Pr 4nBr and Me 4nBr is structure directing agent, has synthesized (Pr respectively 4n) 4ag 4i 8(Me 4n) Ag 2i 3, two compounds are low dimensional structures semiconductor material, and have very strong absorption in visible region to light.(see: G.C.Papavassiliou, G.A.Mousdis, A.TerzisandC.P.Raptopoulou.Z.Naturforsch.1999,54B, 109 – 112);
(2) 2004 years, the people such as Z.R.Chen took DMF as solvent, had synthesized organic hybrid iodo silver hydrochlorate [(EDP) (Ag respectively 2i 4)] n(EDP=N, N '-1,2-ethyl-dipyridinium) and [(EDO) (Ag 2i 4)] n(EDO=N, N '-1,2-ethylence-bis (N, N '-dimethyloctaneammonium), in these two compounds, AgI 4tetrahedron forms one-dimensional catenary structure ion [Ag by co-variation 2i 4] n 2n-.(see: H.H.Li, Z.R.Chen, C.C.Huang, Y.G.RenandQ.H.Chen, Chin.J.Struct.Chem.2004,23,288 – 291; H.H.Li, Z.R.Chen, C.C.Huang, Y.G.RenandG.C.Xiao, Chin.J.Struct.Chem., 2004,23,1009 – 1012);
(3) 2006 years, the people such as J.Q.Li for structure directing agent, synthesized { [Et with divalence quaternary ammonium salt respectively 3n (CH 2) 4nEt 3] [Ag 4i 6] n, { [Et 3n (CH 2) 6nEt 3] [Ag 5i 7] n{ [Me 3n (CH 2) 6nMe 3] [Ag 4i 6] n, these compounds have photoluminescent property, and three compounds show strong fluorescent emission at 438nm, 492nm and 445nm respectively.(see: H.H.Li, Z.R.Chen, J.Q.Li, C.C.Huang, Y.F.ZhangandG.X.Jia, Cryst.GrowthDes., 2006,6,1813 – 1820);
Report about the Pb-Ag iodo hydrochlorate of organic hybrid:
(1) 2006 year, the people such as L.Chen were with PbI 2, AgNO 3, NaI, PPh 3(triphenylphosphine) and Bu 4nI (tetrabutylammonium iodide) is raw material, take DMF as solvent, with Virahol diffusion, has synthesized the silver-colored iodine compound [PbAg of organic hybrid 2(PPh 3) 2i 4] [PbI 2(DMF) 2] and [(Bu 4n) (PbAgI 4)], productive rate is respectively 36.8% and 15.4%.[PbAg 2(PPh 3) 2i 4] and [(PbAgI 4)] –for one-dimensional catenary structure.The two energy gap is respectively 2.82eV and 2.77eV, [(Bu 4n) (PbAgI 4)] there is fluorescence property, maximum emission wavelength is respectively 566nm.（6.L.Q.Fan,L.M.WuandL.Chen.Inorg.Chem.2006,45,3149–3151）。
But, containing PbI 6and AgI 4mixed structure unit and the research with the Pb-Ag Ternary Iodide of coordination organic hybrid has no report.
Summary of the invention
First aspect present invention object is: the problem containing organic cations iodo plumbite and iodo silver hydrochlorate poor heat stability for overcoming tradition, a kind of organic hybrid Pb-Ag hybrid metal iodide of coordination function are provided, it is by the chelating ligands effect of organic constituent and metal, Pb-Ag hybrid metal iodide are made to have different structures and photoelectric property, thus greatly improve the thermostability of iodide, obtain the controlled organic hybrid semiconductor material of energy gap with this.
In order to solve above-mentioned first aspect problem, technical scheme of the present invention is: a kind of organic hybrid Pb-Ag hybrid metal iodide of coordination function, is characterized in that: the general formula of these iodide is [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] n, wherein:
L is the one in following ethylene polyamine part, and L and m meets following condition:
When L is a kind of in quadrol, 1,2-propylene diamine and 1,3-propylene diamine, m=2;
When L is a kind of in N, N, N', N'-Tetramethyl Ethylene Diamine, triethylene tetramine and tetraethylene pentamine, m=1.
Above-mentioned [L in the present invention m(PbAgI 3)] n[L m(PbAg 2i 4)] nn in general formula represents that iodide are ligand polymer, also can replace n with ∞.
Further, when condition one timing, described [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] ntype iodide meet following specific ion coordination structure:
(1) a kind of formed [L in sterically hindered little quadrol, 1,2-propylene diamine and 1,3-propylene diamine is got as L 2(PbAgI 3)] nor [L 2(PbAg 2i 4)] nin type iodide:
At [L 2(PbA gi 3)] nin type compound, [Ag 2i 6] 4 –by I atom and [PbL 2] 2+in Pb (II) ionic bond, formed two dimension [PbAgI 3] nskeleton structure; At [L 2(PbAg 2i 4)] nin type compound, [Ag 2i 4 2 –] none dimension ion is by I atom and [PbL 2] 2+in Pb (II) ionic bond, form three-dimensional [PbAg 2i 4] nskeleton structure;
Each Pb (II) ion has two ethylene polyamine ligand L to be combined by coordinate bond with it in above-mentioned arbitrary skeleton structure, Pb (II) ion is 8 coordination structures;
(2) when L gets sterically hindered comparatively large and N that the coordination number of teeth is higher, a kind of formed [L (PbAgI in N, N', N'-Tetramethyl Ethylene Diamine, triethylene tetramine and tetraethylene pentamine 3)] nor [L (PbAg 2i 4)] nin type iodide:
[PbAgI 3] nthere is two-dimensional framework structure, [PbAg 2i 4] nhave three dimensional skeletal structure, each Pb (II) ion has an ethylene polyamine ligand L to be combined by coordinate bond with it in described arbitrary skeleton structure, Pb (II) ion is 6 – 8 coordination structures; Due to larger sterically hindered of organic ligand, [Ag 2i 6] 4 –[Ag 2i 4 2 –] nwith [PbL] 2+in Pb (II) ionic bond power weaken, Pb – I bond distance is increased, thus improve silver for iodate ion and Pb (II) ionic bond intensity.Namely silver-colored in iodate ion and Pb (II) ionic bond intensity by the steric interference that organic ligand is larger.
A second aspect of the present invention object is to provide a kind of preparation method of organic hybrid Pb-Ag hybrid metal iodide of coordination function, and it, to have the ethylene polyamine part of coordination function for template (structure directing agent), utilizes I –the bridging effect of ion, makes PbI 6and AgI 4structural unit is polymerized under solvent thermal condition, generates hybrid metal iodo-acid salt compound, and by changing reactant amount ratio, obtains the iodide of different structure.The method is by single step reaction synthesis hybrid metal iodide, and it is convenient that synthesis is simple, reaction raw materials is easy to get, product separation is purified, and yield is high, and product structure is clear and definite.
In order to solve above-mentioned second aspect problem, technical scheme of the present invention is: by PbI 2, AgI, KI mix in organic solvent according to the mol ratio of 2:1:4 ~ 1:2:4, add ethylene polyamine ligand L, the consumption volume ratio guaranteeing ethylene polyamine part consumption and organic solvent is 1:2 ~ 1:3, stirs, in a kettle. in 80-100 DEG C of reaction 2-4 days; After reacting complete cool to room temperature, have a large amount of solid to separate out, filter, filter cake priority ethanol and 2-butanone washing, drain, the solid obtained is [L m(PbAgI 3)] ntype product;
Or, improve the consumption of AgI, by PbI 2, AgI, KI mix in organic solvent according to the mol ratio of 1:3:6 ~ 1:4:6, add ethylene polyamine ligand L, the consumption volume ratio guaranteeing ethylene polyamine part consumption and organic solvent is 1:2 ~ 1:3, stirs, in a kettle. in 80-100 DEG C of reaction 2-4 days; After reacting complete cool to room temperature, have a large amount of solid to separate out, filter, filter cake priority ethanol and 2-butanone washing, drain, the solid obtained is [L m(PbAg 2i 4)] ntype product;
Wherein: described organic solvent is a kind of or the two volume ratio in N, N'-dimethyl formamide, methyl-sulphoxide is the mixing solutions of 1:1;
Ethylene polyamine ligand L is selected from the one in quadrol, 1,2-propylene diamine, 1,3-propylene diamine, N, N, N', N'-Tetramethyl Ethylene Diamine, triethylene tetramine, tetraethylene pentamine.
Preferably, PbI described in the present invention 2be 1:1.2 ~ 1:3.5 with the mol ratio of ethylene polyamine ligand L.
Advantage of the present invention is:
1. the present invention is to have the ethylene polyamine of chelating ligands function as part, utilizing the coordination of itself and lead ion, synthesizing the Pb-Ag hybrid metal iodide containing having coordination function organic hybrid under solvent thermal condition.Building-up reactions one step completes, and synthesis material is easy to get, and product separation is purified convenient, and yield is high, product structure is clear and definite, and by the coordination mode of the structural change iodo silver hydrochlorate ion of organic ligand L and lead ion and coordination ability, thus can regulate and control product structure and photoelectric properties.
2. the Pb-Ag hybrid metal iodide of a kind of coordination function organic hybrid of the present invention obtain through single step reaction, and synthesis is simple, and reaction raw materials is easy to get.This compounds has two-dimensional layer or three-dimensional netted Pb-Ag-I ternary skeleton structure, ethylene polyamine is by Pb (II) ionic bond in coordinate bond and Pb-Ag-I inorganic layer, under chelate effect effect, improve the thermostability of organic hybrid metal iodo-acid salt compounds.Utilize the sterically hindered and number of teeth of ethylene polyamine part can not only control the content of organic constituent in product, and affect coordination mode and the binding ability of iodo silver acid ion and Pb (II) ion, make Pb-Ag hybrid metal iodide have different structures and photoelectric property, obtain the organic hybrid semiconductor material that energy gap is controlled.
Embodiment
The abbreviation related in following embodiment is explained as follows:
En is quadrol; Pda is 1,2-propylene diamine; Dap is 1,3-propylene diamine;
Tmeda is N, N, N', N'-Tetramethyl Ethylene Diamine; Trien is triethylene tetramine; Tepa is tetraethylene pentamine;
DMSO is methyl-sulphoxide; DMF is N, N'-dimethyl formamide.
Embodiment one: product chemistry formula is [(en) 2(PbAgI 3)] n, its concrete preparation method is as follows:
By PbI 2(0.462 gram, 1.0 mmoles), AgI(0.117 gram, 0.5 mmole) and KI(0.332 gram, 2 mmoles) join in 2 milliliters of DMSO and 1 milliliter quadrol (en) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 100 DEG C of reactions 2 days.After cool to room temperature, separate out light yellow crystal, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.35 gram, crystal, productive rate 86%.Ultimate analysis: C5.75, H1.79, N6.76%, C 4h 16n 4pbAgI 3theoretical value: C5.89, H1.98, N6.87%.Infrared absorption spectrum data (KBr, cm -1): 3671 (s), 3547 (s), 3247 (s), 3120 (s), 2938 (s), 2869 (s), 1600 (s), 1582 (s), 1486 (s), 1381 (m), 1328 (m), 1316 (m), 1159 (w), 1099 (w), 1080 (s), 1028 (s), 821 (w), 640 (m), 514 (w), 441 (m), 402 (w). solid state absorption spectrometry: semiconductor energy gap E g=2.87eV.N 2under gas atmosphere, decomposition temperature is 210 DEG C.
Embodiment two: product chemistry formula is [(en) 2(PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), AgI (0.468 gram, 2.0 mmoles) and KI (0.498 gram, 3 mmoles) join in 3 milliliters of DMSO and 1 milliliter quadrol (en) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 100 DEG C of reactions 3 days.After cool to room temperature, separate out yellow crystals, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.41 gram, crystal, productive rate 78%.Ultimate analysis: C4.51, H1.46, N5.08%, C 4h 16n 4pbAg 2i 4theoretical value: C4.57, H1.53, N5.33%.Infrared absorption spectrum data (KBr, cm -1): 3392 (w) 3292 (s) 3231 (m) 2921 (w) 2350 (w) 1557 (m) 1456 (w) 1386 (s) 1319 (w) 1097 (w) 1009 (s) 597 (m) 464 (m).Solid state absorption spectrometry: semiconductor energy gap E g=2.57eV.N 2under gas atmosphere, decomposition temperature is 208 DEG C.
Embodiment three: product chemistry formula is [(pda) 2(PbAgI 3)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), AgI (0.234 gram, 1.0 mmoles) and KI (0.332 gram, 2 mmoles) join in 2 milliliters of DMF and 1 milliliters of 1,2-propylene diamine (pda) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 80 DEG C of reactions 4 days.After cool to room temperature, separate out light yellow crystal, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.37 gram, crystal, productive rate 87%.Ultimate analysis: C8.41, H2.31, N6.50%, C 6h 20n 4pbAgI 3theoretical value: C8.54, H2.39, N6.64%.Infrared absorption spectrum data (KBr, cm -1): 3308 (s), 3220 (s), 3122 (s), 2933 (s), 2874 (s), 1582 (s), 1510 (m), 1384 (m), 1329 (m), 1156 (w), 1114 (w), 1029 (s), 1000 (s), 949 (s), 810 (w), 603 (m), 574 (m), 481 (m), 452 (m). solid state absorption spectrometry: semiconductor energy gap E g=2.85eV.N 2under gas atmosphere, decomposition temperature is 219 DEG C.
Embodiment four: product chemistry formula is [(dap) 2(PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), AgI(0.468 gram, 2.0 mmole) and KI(0.498 gram, 3 mmoles) join in 3 milliliters of DMF and 1 milliliters of 1,3-propylene diamine (dap) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 DEG C of reactions 3 days.After cool to room temperature, separate out yellow crystals, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.44 gram, crystal, productive rate 81%.Ultimate analysis: C6.53, H1.66, N5.04%, C 6h 20n 4pbAg 2i 4theoretical value: C6.68, H1.87, N5.19%.Infrared absorption spectrum data (KBr, cm -1): 3447 (w) 3215 (m) 2848 (m) 1579 (m) 1446 (m) 1374 (s) 1075 (s) 936 (s) 815 (m) 581 (w) 482 (w).Solid state absorption spectrometry: semiconductor energy gap E g=2.51eV.N 2under gas atmosphere, decomposition temperature is 224 DEG C.
Embodiment five: product chemistry formula is [(tmeda) (PbAgI 3)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), AgI (0.234 gram, 1.0 mmoles) and KI (0.332 gram, 2 mmoles) joins 2 milliliters of DMF and 1 milliliter N, N, in N', N'-Tetramethyl Ethylene Diamine (tmeda) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 DEG C of reactions 3 days.After cool to room temperature, separate out light yellow crystal, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.31 gram, crystal, productive rate 76%.Ultimate analysis: C8.78, H1.83, N3.32%, C 6h 20n 4pbAgI 3theoretical value: C8.88, H1.99, N3.45%.Infrared absorption spectrum data (KBr, cm -1): 3050 (w), 2920 (w), 1662 (s), 1582 (m), 1510 (s), 1422 (s), 1338 (w), 1254 (w), 1139 (m), 1097 (m), 844 (s), 772 (m), 726 (s), 662 (m), 502 (w), 422 (m). solid state absorption spectrometry: semiconductor energy gap E g=2.71eV.N 2under gas atmosphere, decomposition temperature is 234 DEG C.
Embodiment six: product chemistry formula is [(trien) (PbAgI 3)] n, its concrete preparation method is as follows:
By PbI 2(0.462 gram, 1.0 mmoles), AgI (0.117 gram, 0.5 mmole) and KI (0.332 gram, 2 mmoles) join in 3 milliliters of DMF and 1.5 milliliter triethylene tetramine (trien) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 DEG C of reactions 3 days.After cool to room temperature, separate out light yellow crystal, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.37 gram, crystal, productive rate 88%.Ultimate analysis: C8.44, H2.20, N6.55%, C 6h 18n 4pbAgI 3theoretical value: C8.56, H2.15, N6.65%.Infrared absorption spectrum data (KBr, cm -1): 3447 (w), 3245 (m), 2847 (s), 2761 (s), 1582 (s), 1460 (s), 1381 (m), 1328 (m), 1155 (m), 1080 (m), 1029 (s), 1009 (s), 945 (m), 841 (m), 790 (m), 511 (w), 446 (m). solid state absorption spectrometry: semiconductor energy gap E g=2.88eV.N 2under gas atmosphere, decomposition temperature is 273 DEG C.
Embodiment seven: product chemistry formula is [(trien) (PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), AgI (0.352 gram, 1.5 mmoles) and KI (0.498 gram, 3 mmoles) join in 3 milliliters of DMF and 1.5 milliliter triethylene tetramine (trien) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 DEG C of reactions 3 days.After cool to room temperature, separate out yellow crystals, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.48 gram, crystal, productive rate 89%.Ultimate analysis: C6.55, H1.57, N5.09%, C 6h 18n 4pbAg 2i 4theoretical value: C6.69, H1.68, N5.20%.Infrared absorption spectrum data (KBr, cm -1): 3425 (w) 3197 (m) 2908 (w) 2223 (w) 1551 (m) 1468 (m) 1374 (s) 1329 (m) 1190 (w) 1136 (s) 1041 (s) 882 (w) 748 (m) 704 (m) 531 (m) 476 (m).Solid state absorption spectrometry: semiconductor energy gap E g=2.49eV.N 2under gas atmosphere, decomposition temperature is 284 DEG C.
Embodiment eight: product chemistry formula is [(tepa) (PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), AgI (0.352 gram, 1.5 mmoles) and KI (0.498 gram, 3 mmoles) join in 3 milliliters of DMF and 1.5 milliliter tetraethylene pentamine (tepa) mixing solutionss, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 DEG C of reactions 3 days.After cool to room temperature, separate out light yellow crystal, filter, successively with cold 5 milliliters of ethanol and the washing of 5 milliliters of 2-butanone (cold ethanol and cold 2-butanone refer to the cooled ethanol of mixture of ice and water and 2-butanone), obtain 0.47 gram, crystal, productive rate 85%.Ultimate analysis: C8.49, H2.01, N6.12%, C 8h 23n 5pbAg 2i 4theoretical value: C8.58, H2.07, N6.25%.Infrared absorption spectrum data (KBr, cm -1): 3232 (s), 3135 (s), 2899 (m), 2835 (m), 2325 (w), 1645 (w), 1565 (m), 1443 (m), 1359 (w), 1312 (m), 1177 (m), 1118 (m), 1004 (s), 941 (s), 882 (m), 818 (s), 607 (m), 527 (m), 490 (m), 422 (w).Solid state absorption spectrometry: semiconductor energy gap E g=2.49eV.N 2under gas atmosphere, decomposition temperature is 344 DEG C.
Above embodiment is only the present invention's some embodiments wherein, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (4)

1. organic hybrid Pb-Ag hybrid metal iodide for coordination function, is characterized in that: the general formula of these iodide is [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] n, wherein:
L is the one in following ethylene polyamine part, and L and m meets following condition:
When L is a kind of in quadrol, 1,2-propylene diamine and 1,3-propylene diamine, m=2;
When L is a kind of in N, N, N', N'-Tetramethyl Ethylene Diamine, triethylene tetramine and tetraethylene pentamine, m=1.
2. the organic hybrid Pb-Ag hybrid metal iodide of a kind of coordination function according to claim 1, is characterized in that described [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] ntype iodide meet following specific ion coordination structure:
(1) a kind of formed [L in sterically hindered little quadrol, 1,2-propylene diamine and 1,3-propylene diamine is got as L 2(PbAgI 3)] nor [L 2(PbAg 2i 4)] nin type iodide:
At [L 2(PbAgI 3)] nin type compound, [Ag 2i 6] 4 –by I atom and [PbL 2] 2+in Pb (II) ionic bond, formed two dimension [PbAgI 3] nskeleton structure; At [L 2(PbAg 2i 4)] nin type compound, [Ag 2i 4 2 –] none dimension ion is by I atom and [PbL 2] 2+in Pb (II) ionic bond, form three-dimensional [PbAg 2i 4] nskeleton structure;
Each Pb (II) ion has two ethylene polyamine ligand L to be combined by coordinate bond with it in above-mentioned arbitrary skeleton structure, Pb (II) ion is 8 coordination structures;
(2) when L gets sterically hindered comparatively large and N that the coordination number of teeth is higher, a kind of formed [L (PbAgI in N, N', N'-Tetramethyl Ethylene Diamine, triethylene tetramine and tetraethylene pentamine 3)] nor [L (PbAg 2i 4)] nin type iodide:
[PbAgI 3] nthere is two-dimensional framework structure, [PbAg 2i 4] nhave three dimensional skeletal structure, each Pb (II) ion has an ethylene polyamine ligand L to be combined by coordinate bond with it in described arbitrary skeleton structure, Pb (II) ion is 6 – 8 coordination structures; Due to larger sterically hindered of organic ligand, [Ag 2i 6] 4 –[Ag 2i 4 2 –] nwith [PbL] 2+in Pb (II) ionic bond power weaken, Pb – I bond distance is increased, thus improve silver for iodate ion and Pb (II) ionic bond intensity.
3. a preparation method for the organic hybrid Pb-Ag hybrid metal iodide of the coordination function as described in claim 1 or 2 any one, is characterized in that:
By PbI 2, AgI, KI mix in organic solvent according to the mol ratio of 2:1:4 ~ 1:2:4, add ethylene polyamine ligand L, the consumption volume ratio guaranteeing ethylene polyamine part consumption and organic solvent is 1:2 ~ 1:3, stirs, in a kettle. in 80-100 DEG C of reaction 2-4 days; After reacting complete cool to room temperature, have a large amount of solid to separate out, filter, filter cake priority ethanol and 2-butanone washing, drain, the solid obtained is [L m(PbAgI 3)] ntype product;
Or, improve the consumption of AgI, by PbI 2, AgI, KI mix in organic solvent according to the mol ratio of 1:3:6 ~ 1:4:6, add ethylene polyamine ligand L, the consumption volume ratio guaranteeing ethylene polyamine part consumption and organic solvent is 1:2 ~ 1:3, stirs, in a kettle. in 80-100 DEG C of reaction 2-4 days; After reacting complete cool to room temperature, have a large amount of solid to separate out, filter, filter cake priority ethanol and 2-butanone washing, drain, the solid obtained is [L m(PbAg 2i 4)] ntype product;
Wherein: described organic solvent is a kind of or the two volume ratio in N, N'-dimethyl formamide, methyl-sulphoxide is the mixing solutions of 1:1;
Ethylene polyamine ligand L is selected from the one in quadrol, 1,2-propylene diamine, 1,3-propylene diamine, N, N, N', N'-Tetramethyl Ethylene Diamine, triethylene tetramine, tetraethylene pentamine.
4. preparation method according to claim 3, is characterized in that described PbI 2be 1:1.2 ~ 1:3.5 with the mol ratio of ethylene polyamine ligand L.
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