CN103641851A - Organic hybrid Pb-Ag mixed metal iodide with coordination function and preparation method thereof - Google Patents

Organic hybrid Pb-Ag mixed metal iodide with coordination function and preparation method thereof Download PDF

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CN103641851A
CN103641851A CN201310593995.2A CN201310593995A CN103641851A CN 103641851 A CN103641851 A CN 103641851A CN 201310593995 A CN201310593995 A CN 201310593995A CN 103641851 A CN103641851 A CN 103641851A
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metal iodide
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CN103641851B (en
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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 an organic hybrid Pb-Ag mixed metal iodide with a coordination function which is characterized by having a general formula of [Lm (PbAgI3)]n or [Lm (PbAg2I4)] n, wherein L is one of the following ethylene polyamine ligands, and L and M satisfy the following conditions: when the L is one of ethylenediamine, 1, 2-propylene amide and 1, 3-propylene amide, m is 2; and when the L is one of N, N, N', N'-tetramethylethylenediamine, triethylene tetramine andtetraethylenepentamine, m is 1. The organic hybrid Pb-Ag mixed metal iodide has different structures and photoelectric properties by chelating coordination effects of organic components and metals, the thermal stability of the organic hybrid Pb-Ag mixed metal iodide is greatly improved, and the energy-gap-controllable organic hybrid semiconducting material is prepared. The invention also provides a preparation method of the organic hybrid Pb-Ag mixed metal iodide, the organic hybrid Pb-Ag mixed metal iodide is synthesized by a one step reaction, and the organic hybrid Pb-Ag mixed metal iodide has the advantages of simple synthesis, easily available reaction raw materials, convenient product separation and purification, high yield and definite product structure.

Description

Organic hybrid Pb-Ag hybrid metal iodide of a kind of coordination function and preparation method thereof
Technical field
The present invention relates to organic hybrid Pb-Ag hybrid metal iodide of a kind of coordination function and preparation method thereof.
Background technology
The iodo plumbite of organic hybrid and iodo silver hydrochlorate are semiconductor material, photoelectric material and the alternating temperature material of excellent property, and its physico-chemical property such as optical, electrical and hot is subject to impact and the control of its organic constituent, therefore at aspects such as Inorganic-Organic Hybrid Material and matrix materials, have broad application prospects.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 carries out self-assembly by common top, common limit or coplanar mode, forms respectively the various [Pb of structure xi y] z–[Ag xi y] z–binary Aggregation ion, their polymerization methods is relevant with organic cations structure and kind with the polymerization degree, therefore can affect iodo plumbite and the iodo sour structure of silver and character 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 in 150 ℃ of temperature ranges of 80 –, because losing organic constituent, decompose, the lower thermostability of iodo hydrochlorate of this organic hybrid has limited its range of application greatly.
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 be 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 polymerization jointly, thus the more complicated [Pb of structure formed xag yi z] n–ternary iodo-acid salt ion.Under the synergy of metal and metal function and Pb – I between Pb – Ag and Ag – I polar link, make this class ternary compound there is abundanter photoelectric property.At present, people, comparing deep research aspect organic hybrid iodo plumbite and organic hybrid iodo silver hydrochlorate, have synthesized plumbous iodine and the silver-colored iodide of a series of these class binary, still, and 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 organic amine OH (CH of the people such as N.Mercier to contain hydroxyl 2) 2nH 2with halo organic amine X-(CH 2) 2nH 2(X=Cl, Br) is structure directing agent, synthesized respectively [HO (the CH with two-dimentional perovskite typed laminate structure 2) 2nH 3] 2pbI 4[X (CH 2) 2nH 3] 2pbI 4.[HO (CH 2) 2nH 3] 2pbI 4for alternating temperature material, in the time of 96 ℃, undergo phase transition, from oblique crystal, become mutually orthorhombic crystal phase, this phase transformation is reversible, exists O – HI and N – HI hydrogen bond action to cause in compound simultaneously.[X (CH 2) 2nH 3] 2pbI 4for good semiconductor material, its energy gap is 2.2eV(referring to N.Mercier, S.Poiroux, A.Riou and P.Batail, Inorg.Chem., 2004,43,8361 – 8366; S.Sourisseau, N.Louvain, W.Bi, N.Mercier, D.Rondeau, F.Boucher, J.-Y.Buzar é and C.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, synthesized respectively containing the cationic iodo plumbite of protonated organic amine [NH 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 ℃, show ionic conductivity, and the specific conductivity in the time of 57 ℃ is 6 * 10 -7s cm -1.(referring to: N.Louvain, W.Bi, N.Mercier, J.-Y.Buzar é, C.Legein and G.Corbel, Dalton Trans., 2007,965 – 970);
(3) 2008 years, the people such as G.C.Guo synthesized the organic compound (EDAMP) with three-dimensional structure 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, the radiation of visible light that is 550nm through wavelength, and compound becomes light green from yellow, and after the rayed that is 300nm through wavelength, becomes again deep green.(referring to: Z.J.Zhang, S.C.Xiang, G.C.Guo, G.Xu, M.S.Wang, J.P.Zou, S.P.Guo and J.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 respectively (Pr 4n) 4ag 4i 8(Me 4n) Ag 2i 3, two compounds are low dimensional structures semiconductor material, and in visible region, light are had to very strong absorption.(referring to: G.C.Papavassiliou, G.A.Mousdis, A.Terzis and C.P.Raptopoulou.Z.Naturforsch.1999,54B, 109 – 112);
(2) 2004 years, the people such as Z.R.Chen be take DMF as solvent, had synthesized respectively organic hybrid iodo silver hydrochlorate [(EDP) (Ag 2i 4)] n(EDP=N, N '-1,2-ethyl-dipyridinium) with [(EDO) (Ag 2i 4)] n(EDO=N, N '-1,2-ethylence-bis (N, N '-dimethyl octane ammonium), in these two compounds, AgI 4tetrahedron forms one-dimensional chain structure ion [Ag by co-variation 2i 4] n 2n-.(referring to: H.H.Li, Z.R.Chen, C.C.Huang, Y.G.Ren and Q.H.Chen, Chin.J.Struct.Chem.2004,23,288 – 291; H.H.Li, Z.R.Chen, C.C.Huang, Y.G.Ren and G.C.Xiao, Chin.J.Struct.Chem., 2004,23,1009 – 1012);
(3) 2006 years, the people such as J.Q.Li be take divalence quaternary ammonium salt as structure directing agent, have synthesized respectively { [Et 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.(referring to: H.H.Li, Z.R.Chen, J.Q.Li, C.C.Huang, Y.F.Zhang and G.X.Jia, Cryst.Growth Des., 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 chain structure.The two energy gap is respectively 2.82eV and 2.77eV, [(Bu 4n) (PbAgI 4)] thering is fluorescence property, maximum emission wavelength is respectively 566nm.（6.L.Q.Fan,L.M.Wu?and?L.Chen.Inorg.Chem.2006,45,3149–3151）。
But, containing PbI 6and AgI 4the research of Pb-Ag Ternary Iodide mixed structure unit and that have coordination organic hybrid has no report.
Summary of the invention
First aspect present invention object is: for overcoming tradition containing the problem of organic cations iodo plumbite and iodo silver hydrochlorate poor heat stability, a kind of organic hybrid Pb-Ag hybrid metal iodide of coordination function are provided, it is by the chelating coordination of organic constituent and metal, make Pb-Ag hybrid metal iodide there is different structures and photoelectric property, thereby greatly improve the thermostability of iodide, with this, obtain the controlled organic hybrid semiconductor material of energy gap.
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 a kind of in following ethylene polyamine part, and L and m meet following condition:
When L is quadrol, 1, during a kind of in 2-propylene diamine and 1,3-propylene diamine, m=2;
When L is N, N, N', during a kind of in 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, and also available ∞ replaces n.
Further, as condition one timing, described [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] ntype iodide meet following specific ion coordination structure:
(1) when L gets sterically hindered little quadrol, 1, a kind of formed [L in 2-propylene diamine and 1,3-propylene diamine 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, form [the PbAgI of two dimension 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;
In above-mentioned arbitrary skeleton structure, on each Pb (II) ion, have two ethylene polyamine ligand L with it by coordinate bond combination, Pb (II) ion is 8 coordination structures;
(2) when L gets the sterically hindered large and higher N of the coordination number of teeth, N, N', a kind of formed [L (PbAgI in 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 framework structure, in described arbitrary skeleton structure, on each Pb (II) ion, have an ethylene polyamine ligand L with it by coordinate bond combination, 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, thereby has improved silver for iodate ion and Pb (II) ionic bond intensity.Silver-colored in iodate ion and Pb (II) ionic bond intensity by the larger sterically hindered impact of organic ligand.
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, its take there is coordination function ethylene polyamine part as template (structure directing agent), utilize I –the bridging effect of ion, makes PbI 6and AgI 4structural unit carries out polymerization 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 synthesized hybrid metal iodide by single step reaction, and it is convenient that synthetic 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 of guaranteeing ethylene polyamine part consumption and organic solvent is 1:2～1:3, stirs, and in reactor, in 80-100 ℃, reacts 2-4 days; React after complete cool to room temperature, have a large amount of solids to separate out, filter, filter cake successively, with ethanol and 2-butanone washing, is drained, and the solid obtaining is [L m(PbAgI 3)] ntype product;
Or the consumption of raising 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 of guaranteeing ethylene polyamine part consumption and organic solvent is 1:2～1:3, stirs, and in reactor, in 80-100 ℃, reacts 2-4 days; React after complete cool to room temperature, have a large amount of solids to separate out, filter, filter cake successively, with ethanol and 2-butanone washing, is drained, and the solid obtaining is [L m(PbAg 2i 4)] ntype product;
Wherein: described organic solvent is N, a kind of in N'-dimethyl formamide, methyl-sulphoxide or mixing solutions that the two volume ratio is 1:1;
Ethylene polyamine ligand L is selected from quadrol, 1,2-propylene diamine, 1,3-propylene diamine, N, N, N', a kind of in N'-Tetramethyl Ethylene Diamine, triethylene tetramine, tetraethylene pentamine.
Preferably, PbI described in the present invention 2with the mol ratio of ethylene polyamine ligand L be 1:1.2～1:3.5.
Advantage of the present invention is:
The present invention using there is chelating coordination function ethylene polyamine as part, utilize the coordination of itself and lead ion, the synthetic Pb-Ag hybrid metal iodide containing thering is 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 can affect by the structural changes of organic ligand L coordination mode and the coordination ability of iodo silver hydrochlorate ion and lead ion, thus regulation 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 synthetic simple, 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, improved 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 there is different structures and photoelectric property, obtain the controlled organic hybrid semiconductor material of energy gap.
Embodiment
The abbreviation relating 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 mono-: product chemical 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 of quadrol (en) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 100 ℃ of reactions 2 days.After cool to room temperature, separate out light yellow crystal, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment bis-: product chemical formula is [(en) 2(PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), (0.468 gram of AgI, 2.0 mmoles) and (0.498 gram of KI, 3 mmoles) join in 3 milliliters of DMSO and 1 milliliter of quadrol (en) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 100 ℃ of reactions 3 days.After cool to room temperature, separate out yellow crystals, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment tri-: product chemical formula is [(pda) 2(PbAgI 3)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), (0.234 gram of AgI, 1.0 mmoles) and (0.332 gram of KI, 2 mmoles) join 2 milliliters of DMF and 1 milliliter 1, in 2-propylene diamine (pda) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 80 ℃ of reactions 4 days.After cool to room temperature, separate out light yellow crystal, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment tetra-: product chemical 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 3 milliliters of DMF and 1 milliliter 1, in 3-propylene diamine (dap) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 ℃ of reactions 3 days.After cool to room temperature, separate out yellow crystals, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment five: product chemical 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) join 2 milliliters of DMF and 1 milliliter of N, N, N', in N'-Tetramethyl Ethylene Diamine (tmeda) mixing solutions, stirs 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 ℃ of reactions 3 days.After cool to room temperature, separate out light yellow crystal, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment six: product chemical formula is [(trien) (PbAgI 3)] n, its concrete preparation method is as follows:
By PbI 2(0.462 gram, 1.0 mmoles), (0.117 gram of AgI, 0.5 mmole) and (0.332 gram of KI, 2 mmoles) join in 3 milliliters of DMF and 1.5 milliliters of triethylene tetramines (trien) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 ℃ of reactions 3 days.After cool to room temperature, separate out light yellow crystal, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment seven: product chemical formula is [(trien) (PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), (0.352 gram of AgI, 1.5 mmoles) and (0.498 gram of KI, 3 mmoles) join in 3 milliliters of DMF and 1.5 milliliters of triethylene tetramines (trien) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 ℃ of reactions 3 days.After cool to room temperature, separate out yellow crystals, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Embodiment eight: product chemical formula is [(tepa) (PbAg 2i 4)] n, its concrete preparation method is as follows:
By PbI 2(0.231 gram, 0.5 mmole), (0.352 gram of AgI, 1.5 mmoles) and (0.498 gram of KI, 3 mmoles) join in 3 milliliters of DMF and 1.5 milliliters of tetraethylene pentamine (tepa) mixing solutions, stir 10 minutes, mixture is put into the stainless steel cauldron of tetrafluoroethylene, 90 ℃ of reactions 3 days.After cool to room temperature, separate out light yellow crystal, filter, successively use cold 5 milliliters of ethanol and 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) washing, 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 ℃.
Above embodiment is only the present invention's part embodiment wherein, but can not therefore 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 a kind of in following ethylene polyamine part, and L and m meet following condition:
When L is quadrol, 1, during a kind of in 2-propylene diamine and 1,3-propylene diamine, m=2;
When L is N, N, N', during a kind of in 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 as condition one timing, described [L m(PbAgI 3)] nor [L m(PbAg 2i 4)] ntype iodide meet following specific ion coordination structure:
(1) when L gets sterically hindered little quadrol, 1, a kind of formed [L in 2-propylene diamine and 1,3-propylene diamine 2(PbAgI 3)] nor [L 2(PbAg 2i 4)] nin type iodide:
At [L 2(PbA gi 3)] nin type compound, [A g2i 6] 4 –by I atom and [PbL 2] 2+in Pb (II) ionic bond, form [the PbAgI of two dimension 3] nskeleton structure; At [L 2(PbAg 2i 4)] nin type compound, [A g2i 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;
In above-mentioned arbitrary skeleton structure, on each Pb (II) ion, have two ethylene polyamine ligand L with it by coordinate bond combination, Pb (II) ion is 8 coordination structures;
(2) when L gets the sterically hindered large and higher N of the coordination number of teeth, N, N', a kind of formed [L (PbAgI in 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 framework structure, in described arbitrary skeleton structure, on each Pb (II) ion, have an ethylene polyamine ligand L with it by coordinate bond combination, Pb (II) ion is 6 – 8 coordination structures; Due to larger sterically hindered of organic ligand, [A g2i 6] 4 –[A g2i 4 2 –] nwith [PbL] 2+in Pb (II) ionic bond power weaken, Pb – I bond distance is increased, thereby has improved 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 of guaranteeing ethylene polyamine part consumption and organic solvent is 1:2～1:3, stirs, and in reactor, in 80-100 ℃, reacts 2-4 days; React after complete cool to room temperature, have a large amount of solids to separate out, filter, filter cake successively, with ethanol and 2-butanone washing, is drained, and the solid obtaining is [L m(PbAgI 3)] ntype product;
Or the consumption of raising 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 of guaranteeing ethylene polyamine part consumption and organic solvent is 1:2～1:3, stirs, and in reactor, in 80-100 ℃, reacts 2-4 days; React after complete cool to room temperature, have a large amount of solids to separate out, filter, filter cake successively, with ethanol and 2-butanone washing, is drained, and the solid obtaining is [L m(PbAg 2i 4)] ntype product;
Wherein: described organic solvent is N, a kind of in N'-dimethyl formamide, methyl-sulphoxide or mixing solutions that the two volume ratio is 1:1;
Ethylene polyamine ligand L is selected from quadrol, 1,2-propylene diamine, 1,3-propylene diamine, N, N, N', a kind of in N'-Tetramethyl Ethylene Diamine, triethylene tetramine, tetraethylene pentamine.
4. preparation method according to claim 3, is characterized in that described PbI 2with the mol ratio of ethylene polyamine ligand L be 1:1.2～1:3.5.
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