CN101712734B - High molecular metal complex containing cluster compounds and preparation method thereof - Google Patents
High molecular metal complex containing cluster compounds and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a material with third-order non-linear optical performance, in particular to a preparation method of a high molecular metal complex containing cluster compounds, comprising the following steps of: (1) forming a polymerizing system by using one of a metacrylic acid ester monomer and a styrene derivative monomer as a monomer together with an evocating agent and a chain transfer agent and carrying out reversible addition-fragmentation chain transfer (RAFT) polymerization to obtain a high molecular polymer; and (2) carrying out the complexation reaction on the metal complex with third-order non-linear optical performance as an initiator and the high molecular polymer obtained in the step (1) to prepare the high molecular metal complex with third-order non-linear optical performance. The high molecular metal complex synthesized by the method simultaneously has the initiator of the complex (third-order non-linear optical performance) and the high molecular metal complex, thereby achieving the goal of modifying or improving the performances of the original complex; and compared with a simply-doped mixture of a high molecule/a metal complex, the high molecular metal complex reduces the phase separation and has more stable performance.
Description
Technical field
The present invention relates to a kind of material, be specifically related to a kind of metal complexes and preparation method thereof with high molecular polymer part with third order non-linear optical property.
Background technology
In the prior art, the research object of third order non-linear optical material has mainly comprised pure inorganic semiconductor material, fullerene, organic cpds, superpolymer and a metal-organic complex.These compounds with third order non-linear optical property differ from one another:
Advantages such as (1) pure inorganic materials is a third order non-linear optical material the earliest, has stable performance, and is anti-aging, and duration of service is long, but unsatisfactory at some aspect of performance, such as, the lasing safety wave band is narrow, can not satisfy broadband lasing safety.
(2) organic non linear optical material especially conjugated highpolymer because of the pi-conjugated system of its bigger delocalization; Have stronger third-order nonlinear optical coefficient and fast response time and become one of the most popular research object of third-order nonlinear optical, but because the delocalization degree of conjugated system is big more, promptly the rigidity of compound is big more; Solvability is poor more; Film-forming properties is also poor more, thereby will make this type conjugated polymer become the full optical device of excellent property, still has difficulties.
(3) a metal-organic complex becomes the recent studies on focus of nonlinear optical material because of having concurrently organic and advantage mineral compound.The introducing of metals ion makes the interaction between metal and the organic ligand that intramolecular charge is distributed and distorts, or the dual metal track that occupies and do not occupy is subjected to displacement, thereby it is active to optimize third-order nonlinear optical.For example, phthalocyanine, naphthalene phthalocyanine, porphyrin class macrocylc compound.This compounds is with its superior third order non-linear optical property optical limiting properties and receiving much concern particularly, but because its transition bandwidth is narrower, poorly soluble, workability is poor, is obstructed in application facet.At present, to this compounds carry out modification main as, replace long chain alkane through big ring edge and improve solvability, so often strengthened synthetic difficulty; People such as D.Wohrle process multilayer film with various phthalocyanine germanium (tin) are complex doped in PMMA, owing to reduced the intermolecular gathering of phthalocyanine, the light amplitude limit is superior to solution state (referring to A.Slodek under the film condition; D.Wohrle, J.J.Doyle, W.Blau; Macromol.Symp.; 2006,235,9).But the defective of this method is to be separated, the less stable of material.
In addition, some transition metal atoms duster compounds have non-linear preferably anti-saturated absorption characteristic and become new type light amplitude limit material.Like closed cubane metal heteronuclear duster compound [n-Bu
4N]
3[MoS
4Ag
3Br
3X] (X=Cl, and I) (referring to: S.Shi, W.Ji, S.H.Tang; J.P.Lang, X.Q.Xin, J.Am.Chem.Soc., 1994; 116,3615.) be the metal sulfur-bearing duster compound of reporting third order non-linear optical property the earliest, its light restriction effect all is much better than C under the same conditions
60Toluene solution.And duster compound [Mo
2S
8Ag
4(PPh
3)
4] (referring to: W.Ji, S.Shi, H.J.Du, P.Ge, S.H.Tang, X.Q.Xin, J.Phys.Chem., 1995,99,17297.) be found to be one of best duster compound of present light limiting effect, its photo threshold is 0.1J/cm
2(photo threshold of soccerballene toluene solution is 1.6J/cm
2).But the performance test of these compounds is all carried out in solution, and for the workability of improving it is processed transparent film, existing report is that it is entrained in (W.Zhang, W.Y, Jiao in the TEB 3K; G.Shi, Y.L.Song, Y.X.Wang, D.J.Liu; Q.Chang, C.Zhang, X.Q.Xin, Opt.Mater.; 2008,31,218), still easy formation of this method is separated.
Therefore, need to seek and a kind ofly not only to have had excellent non-linear optical property but also novel material that good processing characteristics is arranged, realize the device of nonlinear optical material.
Summary of the invention
The object of the invention provide a kind of have a third order non-linear optical property contain high molecular metal complex of duster compound and preparation method thereof.
Referring to accompanying drawing 1; Cardinal principle of the present invention is: metal cluster compound and the good high molecular polymer of film-forming properties with third order non-linear optical property well known in the prior art passed through the end group coordination; Formation has the new polymer complex of third order non-linear optical property; The new polymer complex of this type has kept the third-order nonlinear optical character and the high molecular film forming properties of metal cluster compound, becomes the mould material with third order non-linear optical property.
For achieving the above object, the concrete technical scheme of the present invention is that a kind of preparation method who contains the high molecular metal complex of duster compound may further comprise the steps:
(1) be monomer with a kind of in methacrylate monomers or the styrene derivatives monomer; Constitute polymerization system with initiator, chain-transfer agent; Carry out reversible addition-fracture chain transfer (RAFT) polymerization, obtain high molecular polymer, the end group of gained high molecular polymer has the dithio carbazole; Form sulfydryl through reduction reaction, obtain the high molecular polymer that end group is a sulfydryl;
Said methacrylate monomers is selected from: a kind of in TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, Rocryl 400 or the Rocryl 410;
The monomeric chemical structural formula of said styrene derivatives is as follows:
Said initiator is selected from: Diisopropyl azodicarboxylate (AIBN), 1-1 '-azo cyclohexanenitrile;
Said chain-transfer agent is selected from: dithio carbazole phenyl ester, and its molecular formula is as follows:
(2) be that initiator and step (1) gained end group are the high molecular polymer generation coordination reaction of sulfydryl with metal cluster compound, prepare the high molecular metal complex that contains duster compound with third order non-linear optical property with third order non-linear optical property.
In the technique scheme, the end group of step (1) gained high molecular polymer has the dithio carbazole, can form thiol group through reduction reaction, make the polymer end group can with the metal complexes coordination; The molecular weight of above-mentioned high molecular polymer is 5000～150000.
In the technique scheme; In the step (2); The high molecular polymer instead halogen of end group band sulfydryl and the metal cluster compound end group coordination that contains the multinuclear cluster anions form the high molecular metal complex that contains duster compound with third order non-linear optical property, particularly:
(1) when said metal cluster compound be linear three nuclear duster compound (R
4N)
2[MS
4M
1 2X
2] time, high molecular polymer replaces halogen X and M
1Coordination;
Wherein, M=Mo or W; M
1=Cu, Ag or Au; X=I, Cl or Br; R is selected from: the saturated alkyl of carbonatoms 1～4; L representes high molecular polymer;
(2) when said metal cluster compound be four nuclear duster compound (R
4N)
3[MQS
3M
2 3X
3] time, high molecular polymer replaces halogen X and M
2Coordination;
Wherein, Q=O or S; M=Mo or W; M
2=Cu, Ag or Au; X=I, Cl or Br; R is selected from: the saturated alkyl of carbonatoms 1～4; L representes high molecular polymer;
(3) when said metal cluster compound be five nuclear duster compound (R of chair form configuration
4N)
3[MS
4M
3 4X
4] time, high molecular polymer replaces halogen X and M
3Coordination;
Wherein, M=Mo or W; M
3=Cu, Ag; X=I, Cl or Br; R is selected from: the saturated alkyl of carbonatoms 1～4; L representes high molecular polymer.
In the technique scheme, in the step (2), concrete coordination reaction may further comprise the steps:
According to the ratio of amount of substance, ratio=1 of the amount of substance of high molecular polymer and metal cluster compound: 1～N: 1, wherein N equals M in the metal cluster compound respectively
1, M
2Or M
3Number;, mix with metal cluster compound homogeneous phase in organic solvent as part with high molecular polymer, 40～60 ℃ of heated and stirred are half a hour at least; With sufficient reacting, after purifying, washing obtains having the high molecular metal complex that contains duster compound of third order non-linear optical property.
Said organic solvent is selected from: chloroform, N, a kind of in N '-N or the acetone.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
Adopt the new polymer complex of the inventive method synthetic to have metal cluster compound initiator (third order non-linear optical property) and the good film forming properties of macromolecule ligand concurrently; Thereby reach the target of modifying or improving former title complex performance; Polymer-metal complex is compared with simple adulterated polymer/metal duster compound mixture; Reduced being separated, performance is more stable.
Description of drawings
The schematic diagram of preparation high molecular metal complex among accompanying drawing 1 embodiment;
The ultraviolet spectrogram of metal cluster compound, high molecular polymer and high molecular metal complex among accompanying drawing 2 embodiment one, wherein curve 1 is represented metal cluster compound, and curve 2 is represented high molecular polymer, and curve 3 is represented metal complexes PCM1;
The ultraviolet spectrogram of metal cluster compound, high molecular polymer and high molecular metal complex among accompanying drawing 3 embodiment two, wherein curve 1 is represented metal cluster compound, and curve 2 is represented high molecular polymer, and curve 3 is represented metal complexes PCM2.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment one
(1) preparation of chain-transfer agent dithio benzyl carbazole ester (BCCDT): with the 2g carbazole in the 100ml three-necked bottle with anhydrous DMSO stirring and dissolving; Add the ground KOH of 0.74g again; Room temperature reaction 4 to 5 hours; Up to dissolving fully, in ice-water bath, slowly drip excessive dithiocarbonic anhydride then, reacted 4 to 5 hours.(benzyl bromine: carbazole=1.5mol: 1mol), reaction is spent the night to add the benzyl bromine at last.Product precipitates in a large amount of water separates out, suction filtration, and recrystallization obtains BCCDT 3 times in absolute ethyl alcohol.Ultimate analysis: Anal.Calcd:2.07%; H:4.50%; N:4.20%.Found：C：72.18％；H：4.46％；N：4.33％。Reaction process is as follows:
(2) high molecular polymer 1 is synthetic:
(ratio of amount of substance is 50: 1: 1) adds monomer styrene, initiator Diisopropyl azodicarboxylate AIBN, chain-transfer agent dithio benzyl carbazole ester in proportion in the flask of 50ml, and (20mL) makees solvent with pimelinketone, then vacuum nitrogen filling gas; Three times repeatedly; Under 100 ℃, carried out the RAFT polyreaction 12 hours then, in methanol solution, precipitate then; Filter vacuum-drying.Then the polymkeric substance that obtains is dissolved in acetone soln, drip NaBH
4The aqueous solution, filter, vacuum-drying obtains polymkeric substance 1, its structural formula is as follows:
(3) have the high molecular metal complex PMC1 that contains duster compound synthetic of third order non-linear optical property:
(P1 is Mn=50000) with [(C for polymkeric substance 1
4H
9)
4N]
2[MoOS
3Cu
3I
3] (mol ratio 1: 1) mix in DMF solution, heating (30 ℃, half a hour) is separated out in methyl alcohol then, filters, and repeats repeatedly, and methanol wash liquid detects the absorption peak of duster compound with UV spectrum, disappears until absorption peak.The solid PMC1 that obtains characterizes with infrared, UV spectrum.
The preparation process is as follows:
Ir spectra proves: v (Mo=O), 908cm
-1V (Mo-S), 433cm
-1, the Mo-S-Cu skeleton structure of duster compound is not destroyed in this explanation high molecular metal complex 1.From ultraviolet spectrogram (accompanying drawing 2, wherein curve 1 is represented metal cluster compound, curve 2 is represented high molecular polymer, curve 3 is represented metal complexes PCM1), can find out duster compound [(C
4H
9)
4N]
2[MoOS
3Cu
3I
3] similar with the UV spectrum of high molecular metal complex 1,1 absorption peak is arranged about 410nm, this is by duster compound skeleton [MoOS
3] in the charge transfer transition of S → Mo cause, explain that the duster compound skeleton obtains keeping in high molecular metal complex 1.
Absorb the third-order nonlinear susceptibility χ that obtains with its third-order non-linear of Z-scan mode test
(3)=3.64 * 10
-12Esu.Under the same test condition, [(C
4H
9)
4N]
2[MoOS
3Cu
3I
3] not third-order non-linear absorption.(test solvent: DMF, concentration 1mg/10mL)
| Sample | T 0(％) | β(MKS)10 -11 | χ (3) I(esu)10 -12 | ?χ (3)(esu)10 -12 |
| PMC1(Mn＝50000) | 86.07 | 11.1 | 3.64 | ?3.64 |
Because the monomer of polymerization macromolecule polymkeric substance is the stronger monomer of film forming properties among the embodiment one, so the polymer that obtains is prone to film forming.
Embodiment two:
(1) high molecular polymer 2 is synthetic:
Identical with polymkeric substance 1, with the TEB 3K substituted phenylethylene, the structural formula of resulting polymers 2 is as follows:
(2) high molecular metal complex 2 is synthetic:
(P2 is Mn=150000) with [(C for polymkeric substance 2
4H
9)
4N]
2[MoOS
3Cu
3I
3] (mol ratio 1: 1) mix in DMF solution, in methyl alcohol, separates out then 30 ℃ of heating half a hour, filters, and repeats repeatedly, the solid PMC2 that obtains is with infrared, UV spectrum sign.
The preparation process is as follows:
Ir spectra proves: v (Mo=O), 908cm
-1V (Mo-S), 433cm
-1, the Mo-S-Cu skeleton structure of duster compound is not destroyed in this explanation high molecular metal complex 1.From ultraviolet spectrogram (accompanying drawing 3, wherein curve 1 is represented metal cluster compound, curve 2 is represented high molecular polymer, curve 3 is represented metal complexes PCM2), can find out duster compound [(C
4H
9)
4N]
2[MoOS
3Cu
3I
3] similar with the UV spectrum of high molecular metal complex 2,1 absorption peak is arranged about 410nm, this is by duster compound skeleton [MoOS
3] in the charge transfer transition of S → Mo cause, explain that the duster compound skeleton obtains keeping in high molecular metal complex 2.
Absorb the third-order nonlinear susceptibility χ that obtains with its third-order non-linear of Z-scan mode test
(3)=5.38 * 10
-12Esu.(test solvent: DMF, concentration 1mg/10mL)
| Sample | T 0(％) | β(MKS)10 -11 | χ (3) I(esu)10 -12 | χ (3)(esu)10 -12 |
| PMC2(Mn＝150000) | 87.95 | 16.3 | 5.38 | 5.38 |
Because the monomer of polymerization macromolecule polymkeric substance is the stronger monomer of film forming properties among the embodiment two, so the polymer that obtains is prone to film forming.
Embodiment three
(1) according to the method for embodiment one step (2), adopting the RAFT method to prepare molecular weight is 2000,4000,20000,50000 PS PMC1;
(2), use the PMC1 and the duster compound [Bu of different molecular weight (molecular weight is respectively 2000,4000,20000,50000) according to the method for embodiment one step (3)
4N]
2[MoOS
3Cu
3I
3] preparation series macromolecular metal complexes;
(3) absorb with Z-scan mode test third-order non-linear
Duster compound [Bu
4N]
2[MoOS
3Cu
3I
3] and the non-linear absorption curve of PMC1 in DMF of different molecular weight.The result shows: duster compound [Bu
4N]
2[MoOS
3Cu
3I
3] sample do not have non-linear absorption basically; Polymer-metal complex PMC1 sample then has non-linear absorption, and non-linear absorption is anti-saturated absorption.And, along with polymer P 1 molecular weight increases, with duster compound [Bu
4N]
2[MoOS
3Cu
3I
3] the non-linear anti-saturated absorption of the polymer-metal complex PMC1 that forms also has obvious enhancing, when the molecular weight Mn of polymer P 1＞=50,000, the non-linear anti-saturated absorption of polymer-metal complex PMC1 reaches stable peak (seeing form 3) basically.This shows, at duster compound skeleton [MoOS
3Cu
3] introduce the flexible macromolecule chain on every side, help the enhancing of non-linear absorption.
The third-order non-linear performance data table of form 3 different molecular weight PMC1
| T 0(％) | β(MKS)10 -11 | χ (3) I(esu)10 -12 | χ (3)(esu)10 -12 | |
| PMC1(Mn＝2000) | 79.33 | 0.653 | 0.215 | 0.215 |
| PMC1(Mn＝4000) | 75.24 | 2.98 | 0.981 | 0.981 |
| PMC1(Mn＝20000) | 82.25 | 5.94 | 1.95 | 1.95 |
| PMC1(Mn＝50000) | 86.07 | 11.1 | 3.64 | 3.64 |
Embodiment four
(1) according to the method for embodiment two steps (1), adopts the RAFT method, the high molecular polymer PMC2 of preparation molecular weight 50000;
(2), use PMC2 (Mn=50000) and and duster compound [Bu according to the method for embodiment two steps (2)
4N]
2[MoOS
3Cu
3I
3] the preparation high molecular metal complex;
(3) absorb with Z-scan mode test third-order non-linear
The third-order non-linear performance of test implementation example two and embodiment four gained high molecular metal complexes, the result finds that duster compound [Bu4N] 2 [MoOS3Cu3I3] sample does not have non-linear absorption basically; Polymer-metal complex PMC2 sample then has non-linear absorption, and non-linear absorption is anti-saturated absorption.And along with the increase of the molecular weight of P2, the non-linear absorption of PMC2 is also become better and better.See table 4
The third-order non-linear performance data table of form 4 different molecular weight PMC2
| T 0(％) | β(MKS)10 -11 | χ (3) I(esu)10 -12 | ?χ (3)(esu)10 -12 | |
| PMC2(Mn＝50000) | 81.12 | 6.01 | 1.99 | ?1.99 |
| PMC2(Mn＝150000) | 87.95 | 16.3 | 5.38 | ?5.38 |
Claims (3)
1. a preparation method who contains the high molecular metal complex of duster compound is characterized in that, may further comprise the steps:
(1) be monomer with a kind of in methacrylate monomers or the styrene derivatives monomer; Constitute polymerization system with initiator, chain-transfer agent; Carry out reversible addition-fracture chain transfer polymerization, obtain high molecular polymer, the end group of gained high molecular polymer has the dithio carbazole; Form sulfydryl through reduction reaction, obtain the high molecular polymer that end group is a sulfydryl;
Said methacrylate monomers is selected from: a kind of in TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, Rocryl 400 or the Rocryl 410;
The monomeric chemical structural formula of said styrene derivatives is as follows:
Said initiator is selected from: Diisopropyl azodicarboxylate, 1-1 '-azo cyclohexanenitrile;
Said chain-transfer agent is selected from: dithio carbazole phenyl ester;
(2) be that initiator and step (1) gained end group are the high molecular polymer generation coordination reaction of sulfydryl with metal cluster compound, prepare the high molecular metal complex that contains duster compound with third order non-linear optical property with third order non-linear optical property;
Said metal cluster compound is selected from: linear three nuclear duster compound (R
4N)
2[MS
4M
1 2X
2], four nuclear duster compound (R of closed cubane configuration
4N)
3[MQS
3M
2 3X
3], five nuclear duster compound (R of chair form configuration
4N)
3[MS
4M
3 4X
4], wherein, M=Mo or W; M
1=Cu, Ag or Au; M
2=Cu, Ag or Au; M
3=Cu, Ag; Q=O or S; X=I, Cl or Br; R is selected from: the saturated alkyl of carbonatoms 1～4;
In the step (2), concrete coordination reaction may further comprise the steps:
According to the ratio of amount of substance, ratio=1 of the amount of substance of high molecular polymer and metal cluster compound: 1～N: 1, wherein N equals M in the metal cluster compound respectively
1, M
2Or M
3Number;, mix with metal cluster compound homogeneous phase in organic solvent as part with high molecular polymer, 40～60 ℃ of heated and stirred are half a hour at least; With sufficient reacting, after purifying, washing obtains having the high molecular metal complex that contains duster compound of third order non-linear optical property.
2. preparation method according to claim 1 is characterized in that, the molecular weight of high molecular polymer is 5000～150000.
3. preparation method according to claim 1 is characterized in that, said organic solvent is selected from: chloroform, N, a kind of in N '-N or the acetone.
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| Title |
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| Wang Zhang et al..The non-linear optical properties of the planar metal cluster [MoS4Cu4I2(py)6] doped in PMMA.<Optical Materials>.2008,第31卷(第2期),218-222. * |
| 徐庆锋等.[(η~5-C_5Me_5)WS_3Cu_3Br_2(PPyPh_2)_2]四核簇合物的合成和晶体结构.《高等学校化学学报》.2002,第23卷(第9期),1641-1644. * |
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