CN102134248A - Multi-sulfo-disulfide alkene nickel coordination compound and preparation method and application thereof - Google Patents
Multi-sulfo-disulfide alkene nickel coordination compound and preparation method and application thereof Download PDFInfo
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- CN102134248A CN102134248A CN201110001635XA CN201110001635A CN102134248A CN 102134248 A CN102134248 A CN 102134248A CN 201110001635X A CN201110001635X A CN 201110001635XA CN 201110001635 A CN201110001635 A CN 201110001635A CN 102134248 A CN102134248 A CN 102134248A
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- quinolyl
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 title abstract description 10
- 150000001336 alkenes Chemical class 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 74
- 229930192474 thiophene Natural products 0.000 claims description 37
- 239000000975 dye Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical class [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical group [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 3
- 229960001393 dosulepin Drugs 0.000 abstract 3
- PHTUQLWOUWZIMZ-GZTJUZNOSA-N trans-dothiepin Chemical compound C1SC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 PHTUQLWOUWZIMZ-GZTJUZNOSA-N 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 1
- 150000001450 anions Chemical group 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 150000001768 cations Chemical group 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 abstract 1
- -1 polythio Polymers 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 4
- 241000931526 Acer campestre Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JDRCAGKFDGHRNQ-UHFFFAOYSA-N nickel(3+) Chemical compound [Ni+3] JDRCAGKFDGHRNQ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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Abstract
The invention relates to a nickel coordination compound which is characterized in that the anion part of the nickel coordination compound is a (1, 4) dothiepin (2, 3-b) quinolyl-2, 3-disulfide nickel (II) coordination compound, the cation part is quaternary alkyl R ammonium positive ions, and the nickel coordination compound has the following structural formula. The (1, 4) dothiepin (2, 3-b) quinolyl-2, 3-disulfide nickel (II) coordination compound is simple in composition, and beneficial to purification, has higher yield, good stability in the air, can be used as near-infrared laser dimming Q dye, and the measured near-infrared absorption data indicates that the maximal absorption peak of the (1, 4) dothiepin (2, 3-b) quinolyl-2, 3-disulfide nickel (II) acid tetrabutyl ammonium is 1082nm, which is extremely approximate to the laser wavelength of Nd: YAG laser and Nd: YAP laser. The nickel coordination compound can be applied to the aspects of near-infrared laser dimming Q dye, laser protective materials and the like. The invention also discloses the preparation method of the nickel coordination compound.
Description
Technical field
The present invention relates to two sulphur alkene title complexs of nickel, also relate to near-infrared laser and transfer Q dyestuff and laser protective material.
Background technology
Hear-infrared absorption dye is a class important function dyestuff, is meant that mainly absorbing wavelength drops on near-infrared region (〉 700 nm) functional dye, comprise cyanines class, phthalocyanines, metal complexes class, quinoid, azo class etc.Because advantages such as inexpensive, good stability, making are simple, environmentally friendly and have a extensive future, they have been subjected to the extensive concern of countries in the world.
Two sulphur alkene shaped metal title complexs are a kind of of nir dye, since beginning development the sixties in 20th century, its be subjected to widely paying close attention to [referring to (a) K. H. Drexhage and U. T. Muller-Westerhoff,
IEEE J. Quantum Electron, QE-8,1972,759; (b) C. S. Winter, S. N. Oliver, R. J. Manning, J. D. Rush, C. A. S. Hill and A. E. Underhill,
J. Mater. Chem., 1992,2,443; (c) F. Bigoli, P. Deplano, F. A. Devillanova, U. Lippolis, P. J. Lukes, M. L. Mercuri, M. A. Pellinghelli and E. F. Trogu,
J. Chem. Soc., Chem. Commun., 1995,371; (d) M. Arca, F. Demartin, F. A. Devillanova, A. Garau, F. Isaia, F. Lelj, V. Lippolis, S. Pedraglio and G. Verani,
J. Chem. Soc., Dalton Trans., 1998,3731].This metal complexes can make maximum absorption band λ max move in 600～1400 nm even higher wave band [referring to (a) J. L. Zuo by means such as molecular modifications, T. M. Yao, F. You, X. Z. You, H. K. Fun and B. Yip
J. Mater.Chem., 1996,6,1633; (b) Yang Xiaobing, the fourth soughing of the wind in the pines, Yang Yusheng etc., organic chemistry, 2002,22,33].Their general photo and thermal stabilities are better, but also have good air stability.As a kind of effective infrared absorbing agents, two sulphur alkene shaped metal title complexs not only can be used as dye well coating, but also can be used as the infrared absorbent of transparent material, its special light, electricity, magnetic property have broad application prospects at aspects such as liquid crystal, superconduction, laser Q-switching and protective materials [referring to (a) M. Bousseau, L. Valade, J.-P. Legros, P. Cassoux, M. Garbauskas and L. V. Interrante
J. Am. Chem. Soc., 1986,100,1908; (b) A. E. Pullen and R.-M. Olk,
Coord. Chem. Rev., 1999,211,188].
The generation of laser Q-switching technology and development are the important breakthrough on the laser development history.Laser apparatus can obtain the giant pulse of narrow pulsewidth, high-peak power by transferring Q.The acquisition of this giant pulse has promoted laser processing, range finding, radar, has taken pictures and the development of many technical fields such as high light optics at a high speed.As the prerequisite of transferring the Q dyestuff be: 1. dyestuff should have intensive saturated absorption characteristic to optical maser wavelength, and promptly dyestuff absorption peak centre wavelength is identical substantially with the excitation wavelength of laser apparatus; 2. dyestuff absorption bandwidth deltaf δ is narrow as far as possible, otherwise can influence the Q switch efficiency; 3. dyestuff should have good photochemical stability; 4. suitable saturated light intensity will be arranged.
For the laser apparatus of optical maser wavelength in infrared territory, as the Nd:YAG laser apparatus (
l L=1064 nm) and the Nd:YAP laser apparatus (
l L=1079 nm), their corresponding dyestuffs because it is few to absorb the color development system of infrared light, thus can reach transfer Q and the technical requirements of locked mode dyestuff just still less.Be applied to the accent Q locked mode dyestuff of infrared territory laser apparatus at present, mainly contain cyanine dyes and sulfo-diene transition metal complex [referring to (a) G. A. Reynolds and K. H. Drexhage,
J. Org. Chem., 1977,42,885; (b) R. C. Greenhow, D. M. Goodall and R. W. Eason,
Chem. Phys., 1984,83,445].This two classes dyestuff is compared, and cyanine dyes is the dyestuff that is applied to transfer Q and locked mode the earliest, and its absorbing wavelength can the red shift by the length that increases methine chain, but because the growth of chain, light stability is poor, brings restriction to practical application.Two sulphur alkene shaped metal title complexs can reach the less of locked mode requirement, but because the absorption of its long wave is relevant with metal ion, and the molecular structure planarity is good, light stability is better, is the accent Q locked mode dyestuff of potential excellent property.
Summary of the invention
The title complex that the purpose of this invention is to provide a kind of nickel, it can be used for near-infrared laser and transfer the lasing safety of Q dye well.
Technical scheme of the present invention is as follows:
A kind of title complex of nickel, its anionicsite are also [2,3-b] quinolyls-2 of [1,4] two thiophene English, 3-disulfido nickel (
II) title complex, cationic moiety are the tetra-allkylammonium positive ion, and it has following structural formula:
The title complex of above-mentioned nickel, described alkyl (R) is the alkyl of 1-4 carbon.
A kind of method for preparing the title complex of above-mentioned nickel, it comprises the following steps:
Above-mentioned preparation method, described halogenation tetra-allkylammonium is iodate tetramethyl-ammonium, tetraethylammonium bromide, bromination tetrapropyl ammonium or Tetrabutylammonium bromide.
[1,4] of the present invention two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) sour TBuA is transferred the Q dyestuff as near-infrared laser, and it is as follows to record data: at N, in the dinethylformamide solution, maximum absorption wavelength is 1082 nm in the near-infrared region, and molar extinction coefficient is 15000 dm
3Mol
-1Cm
-1This result shows: the present invention [1,4] two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) 4-butyl ammonium of title complex has the performance that near-infrared laser is transferred the Q dyestuff, has application prospect at aspects such as near infrared absorbent, laser Q-switching material, lasing safeties.
With ultimate analysis (C, H, N), infrared, ultraviolet, electron paramagnetic resonance, X-ray single crystal diffraction characterize and confirmed also [2,3-b] quinolyl-2 of [1,4] two thiophene English, 3-disulfido nickel (
II) structure of sour TBuA.Detecting used instrument is: Perkin-Elmer 240C type elemental analyser, Vector22 Bruker spectrophotometer (400-4000 cm
-1), UV-3100 type ultraviolet-visible spectrophotometer, Bruker ER 200-D-SRC spectrophotometer and Bruker Smart Apex CCD single crystal diffractometer etc.
[1,4] of the present invention two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) complex dye maximum absorption band λ max is at 1082 nm, and very near the optical maser wavelength (being respectively 1064 nm and 1079 nm) of Nd:YAG laser apparatus and Nd:YAP laser apparatus, the absorption intensity at 1064 nm and 1079 nm places is respectively 14800 dm
3Mol
-1Cm
-1With 15000 dm
3Mol
-1Cm
-1Compare with cyanine dyes, its photo and thermal stability is better; Compare with other neutral polythio two sulphur alkene transition metal complexes, solvability is better, but also has good air stability.[1,4] of the present invention two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) sour TBuA is synthetic simple, is convenient to purify, and productive rate is higher, and property stable in the air is good; We can update the physicochemical property of this class thio diene nickel (III) title complex by the modification of part, and they have broad application prospects at aspects such as coating, liquid crystal, laser Q-switching material, near infrared absorption and laser protective materials.
Description of drawings
Fig. 1 is the uv-visible absorption spectra of title complex of the present invention.
Fig. 2 is the electron paramagnetic resonance spectrum figure of title complex of the present invention.
Fig. 3 is the anionic single crystal structure figure of invention title complex.
Embodiment
Embodiment one: [1,4] two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) preparation of sour TBuA
1.1 ', 3
'
-dithio [4
'
, 5 ': 5,6] the also preparation of [2,3-b] quinolyl-2-ketone of [1,4] two thiophene English:
With 1
', 3
'-dithio [4
', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-thioketones (810 mg, 2.5 mmol) and mercuric acetate (2.39 g, 7.5 mmol) mix, stirred 6 hours after adding 70 mL Glacial acetic acid and 210 ml trichloromethanes, filter, filtrate is washed, is washed with saturated sodium bicarbonate, and the organic phase anhydrous magnesium sulfate drying filters, concentrate, obtain yellow solid 1
', 3
'-dithio [4
', 5
': 5,6] [1,4] two thiophene English [2,3-b] quinolyl-2-ketone 0.54 g also, productive rate 70%.Compound is through ultimate analysis, mass spectrum, the infrared checking, and the result shows that structure is correct, and data are as follows:
Results of elemental analyses: calculated value: C (%): 42.84 H (%): 1.31 N (%): 9.08 O (%): 5.19
Measured value: C (%): 42.78 H (%): 1.29 N (%): 9.10 O (%): 5.12
EI-MS:?m/z 307.8(M
+)
IR(KBr)?(n
max,?cm
-1):1688?(C=O)
2. [1,4] two thiophene English [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) preparation of sour TBuA:
Under nitrogen protection, to 1
', 3
'-dithio [4
', 5
': 5,6] [1,4] two thiophene English also [2,3-b] ethanolic soln (10 mL) of dropping sodium (88 mg, 2.2 mmol) in the quinolyl-2-ketone (308 mg, 1 mmol), get orange clear liquid, in orange clear liquid, dropwise add the ethanolic soln (10 mL) of Nickel dichloride hexahydrate (118 mg, 0.5 mmol), reacted 2 hours, expose and continue in the air to stir 0.5 hour, solution becomes brown by purple, filters, and adds Tetrabutylammonium bromide (500 mg in filtrate, 1.5 ethanolic soln mmol) (8 mL), filter, obtain brown solid 237 mg, productive rate 55%.Compound verifies that through ultimate analysis, infrared, ultraviolet the result shows that structure is correct, and data are as follows:
Results of elemental analyses: calculated value: C (%): 50.16 H (%): 5.14 N (%): 8.12
Measured value: C (%): 50.09 H (%): 5.18 N (%): 8.19
IR?(KBr)?(n
max,?cm
-1)：2956,?2869,?1555,?1474,?1328,?1174,?1110,?871,?755,?597,?467.
UV-Vis (DMF): λ
Max/ nm (ε/dm
3Mol
-1Cm
-1)=1086 (15000) (accompanying drawing 1)
Tetrabutylammonium bromide substituted with iodate tetramethyl-ammonium, tetraethylammonium bromide or bromination four n-propyl ammoniums respectively to obtain cationic moiety respectively be [1 of tetramethyl-ammonium, tetraethyl ammonium or four n-propyl ammoniums, 4] two thiophene English also [2,3-b] quinolyl-2,3-disulfido nickel (
II) title complex.
Embodiment two: [1,4] of the present invention two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) electron paramagnetic resonance of sour TBuA characterizes
Testing tool is a Bruker ER 200-D-SRC spectrometer.Title complex solid of the present invention is measured under 110 K conditions: g
1=2.062, g
2=2.012(sees accompanying drawing 2).
Embodiment three: [1,4] of the present invention two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) single crystal structure of sour TBuA characterizes
Testing tool is a Bruker Smart Apex CCD single crystal diffractometer, with Mo-Ka (l=0.071073 nm) ray, tests with the scan pattern of w/2q when 20 ° of C.More multidata is then revised by SAINT, and Lorentz revises and the elimination of polarizing effect obtains.Absorbing the SADABS that revises use Bruker replenishes.Directly solved molecular structure with SHELXL-97.Measure with the method for direct E-maps the position of the atoms metal and the atom that links to each other on every side thereof, and other non-hydrogen atoms are by Fourier transform, and its fine structure is progressively determined in least-squares refinement.Hydrogen atom then is determined at the position of calculating gained at last, and unified U is arranged
IsoValue (accompanying drawing 3).
These results show that [1,4] of the present invention two thiophene English are [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) 4-butyl ammonium of title complex has the performance of nir dye, is the Q-switch and mode-locking dyestuff and the laser protective material of potential excellent property.
Claims (5)
1. the title complex of a nickel, it is characterized in that: its anionicsite is also [2,3-b] quinolyls-2 of [1,4] two thiophene English, 3-disulfido nickel (
II) title complex, cationic moiety are the tetra-allkylammonium positive ion, and it has following structural formula:
2. the title complex of pinching according to claim 1 is characterized in that: described alkyl (R) is the alkyl of 1-4 carbon.
3. a method for preparing the title complex of the described nickel of claim 1 is characterized in that it comprises the following steps:
Step 1, with 1 ', 3
'-dithio [4
', 5
': 5,6] also [2,3-b] quinolyl-2-thioketones and the mercuric acetate mixing of [1,4] two thiophene English, stirred 6 hours behind adding Glacial acetic acid and the trichloromethane, the amount of adding is per 2.5 mmoles 1 ', 3
'-dithio [4
', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-thioketones add mercuric acetate 7.5 mmoles, per 2.5 mmoles 1 ', 3
'-dithio [4
', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-thioketones add 70 milliliters in Glacial acetic acid, per 2.5 mmoles 1 ', 3
'-dithio [4
', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-thioketones add 210 milliliters of trichloromethanes, filter, filtrate is washed, is washed with saturated sodium bicarbonate, the organic phase anhydrous magnesium sulfate drying filters, and is concentrated, obtains yellow solid 1 ', 3 '-dithio [4 ', 5
': 5,6] [1,4] two thiophene English [2,3-b] quinolyl-2-ketone also;
Step 2, under nitrogen protection, in step 11 ' of gained, 3 '-dithio [4 ', 5
': 5,6] [1,4] two thiophene English ethanolic soln of dropping sodium in [2,3-b] quinolyl-2-ketone also, the amount of adding is per 1 mmole, 1 ', 3 '-dithio [4 ', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-ketone hydro-oxidation sodium 2.2 mmoles, per 2.2 mmole sodium hydroxide add 10 milliliters of ethanol, get orange clear liquid, the ethanolic soln that in orange clear liquid, dropwise adds Nickel dichloride hexahydrate, the amount that adds is per 1 mmole, 1 ', 3 '-dithio [4 ', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-ketone adds 0.5 mmole Nickel dichloride hexahydrate, per 0.5 mmole Nickel dichloride hexahydrate adds 10 milliliters of ethanol, reacts 2 hours, exposes to continue in the air to stir 0.5 hour, solution becomes brown by purple, filter, add the ethanolic soln of halogenation tetraalkyl base ammonium in filtrate, the amount of adding is per 1 mmole 1 ', 3 '-dithio [4 ', 5
': 5,6] [1,4] two thiophene English also [2,3-b] quinolyl-2-ketone add 1.5 mmole Tetrabutylammonium bromides, per 1.5 mmole Tetrabutylammonium bromides add 8 milliliters of ethanol, filter, and obtain brown solid, are of the present invention [1,4] two thiophene English [2,3-b] quinolyl-2 also, 3-disulfido nickel (
II) 4-butyl ammonium of title complex.
4. preparation method according to claim 3 is characterized in that: described halogenation tetra-allkylammonium is iodate tetramethyl-ammonium, tetraethylammonium bromide, bromination tetrapropyl ammonium or Tetrabutylammonium bromide.
5. the application of the title complex of the described nickel of claim 1 in preparation near infrared accent Q dyestuff and laser protective material.
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| CN104926887A (en) * | 2015-06-11 | 2015-09-23 | 泰山医学院 | Synthetic method of mixed ligand coordination planar metal disulfide ene complex |
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| CN104347903A (en) * | 2013-08-07 | 2015-02-11 | 通嘉科技股份有限公司 | Method for charging rechargeable battery |
| CN104347903B (en) * | 2013-08-07 | 2017-03-01 | 通嘉科技股份有限公司 | Charging method to Rechargeable battery |
| CN103483391A (en) * | 2013-09-25 | 2014-01-01 | 中国科学院长春应用化学研究所 | Strong near-infrared absorption polysulfide metal complex as well as preparation method and application thereof |
| CN103483391B (en) * | 2013-09-25 | 2016-12-07 | 中国科学院长春应用化学研究所 | Near-infrared light intensity absorption many sulfur metals coordination compound and preparation method and application |
| CN104926887A (en) * | 2015-06-11 | 2015-09-23 | 泰山医学院 | Synthetic method of mixed ligand coordination planar metal disulfide ene complex |
| CN104926887B (en) * | 2015-06-11 | 2017-07-21 | 泰山医学院 | A kind of synthetic method of mixed ligand coordinated planar metal dithionite alkene complex |
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