CN102134248B - 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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- CN102134248B CN102134248B CN 201110001635 CN201110001635A CN102134248B CN 102134248 B CN102134248 B CN 102134248B CN 201110001635 CN201110001635 CN 201110001635 CN 201110001635 A CN201110001635 A CN 201110001635A CN 102134248 B CN102134248 B CN 102134248B
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- quinolyl
- nickel
- dithio
- nitrae
- isosorbide
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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 the important functional dye of a class, refers to that mainly absorbing wavelength drops on near-infrared region (〉 700 nm) functional dye, comprise cyanines class, phthalocyanines, metal complexes class, quinoid, azo etc.Because advantages such as inexpensive, good stability, making are simple, environmentally friendly and have a extensive future, they have been subject 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 subject 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 mobile 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 is by transferring Q can obtain the giant pulse of narrow pulsewidth, high-peak power.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 strong saturated absorption characteristic to optical maser wavelength, and namely dyestuff absorption peak centre wavelength is substantially identical with the excitation wavelength of laser apparatus; 2. dyestuff Absorber Bandwidth Δ δ is as far as possible narrow, otherwise can affect 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 at present the accent Q locked mode dyestuff of infrared territory laser apparatus, 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 the earliest transfer Q and locked mode, 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 its long wave absorbs relevantly with metal ion, and the molecular structure planarity is good, and light stability is better, are the accent Q locked mode dyestuffs of potential excellent property.
Summary of the invention
The purpose of this invention is to provide a kind of complexes 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 complexes of nickel, its anionicsite are also [2,3-b] quinolyls-2 of [Isosorbide-5-Nitrae] two thiophene English, 3-disulfido nickel (
II) title complex, cationic moiety are the tetra-allkylammonium positive ion, and it has following structural formula:
Above-mentioned complexes of nickel, described alkyl (R) is the alkyl of 1-4 carbon.
A kind of method for preparing above-mentioned complexes of 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.
[Isosorbide-5-Nitrae] 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 data measured is as follows: in DMF 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's [Isosorbide-5-Nitrae] 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.
Characterize and confirmed also [2,3-b] quinolyl-2 of [Isosorbide-5-Nitrae] two thiophene English with ultimate analysis (C, H, N), infrared, ultraviolet, electron paramagnetic resonance, X-ray single crystal diffraction, 3-disulfido nickel (
II) structure of sour TBuA.The detection 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.
[Isosorbide-5-Nitrae] 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.[Isosorbide-5-Nitrae] 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 single crystal structure figure of invention title complex negatively charged ion.
Embodiment
Embodiment one: [Isosorbide-5-Nitrae] 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 [Isosorbide-5-Nitrae] two thiophene English:
With 1
', 3
'-dithio [4
', 5
': 5,6] [Isosorbide-5-Nitrae] 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, concentrated, obtain yellow solid 1
', 3
'-dithio [4
', 5
': 5,6] [Isosorbide-5-Nitrae] 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. [Isosorbide-5-Nitrae] 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] the middle ethanolic soln (10 mL) that drips sodium hydroxide (88 mg, 2.2 mmol) of quinolyl-2-ketone (308 mg, 1 mmol), get orange clear liquid, dropwise add the ethanolic soln (10 mL) of Nickel dichloride hexahydrate (118 mg, 0.5 mmol) in the orange clear liquid, reacted 2 hours, continue in the exposure 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 respectively cationic moiety 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: [Isosorbide-5-Nitrae] 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 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: [Isosorbide-5-Nitrae] 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 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 data 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 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 [Isosorbide-5-Nitrae] 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 that the Q-switch and mode-locking of potential excellent property is with dyestuff and laser protective material.
Claims (3)
1. complexes of nickel, it is characterized in that: its anionicsite is also [2,3-b] quinolyls-2 of [Isosorbide-5-Nitrae] two thiophene English, 3-disulfido nickel (III) title complex, cationic moiety is the tetra-allkylammonium positive ion, it has following structural formula:
2. a method for preparing complexes of nickel claimed in 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 mercuric acetate mixing of [Isosorbide-5-Nitrae] two thiophene English, stirred 6 hours after adding Glacial acetic acid and trichloromethane, the amount of adding is per 2.5 mmoles, 1 ', 3 '-dithio [4 ', 5 ': 5,6] [Isosorbide-5-Nitrae] two thiophene English also [2,3-b] quinolyl-2-thioketones adds mercuric acetate 7.5 mmoles, per 2.5 mmoles, 1 ', 3 '-dithio [4 ', 5 ': 5,6] [Isosorbide-5-Nitrae] two thiophene English also [2,3-b] quinolyl-2-thioketones adds 70 milliliters in Glacial acetic acid, per 2.5 mmoles, 1 ', 3 '-dithio [4 ', 5 ': 5,6] [Isosorbide-5-Nitrae] two thiophene English also [2,3-b] quinolyl-2-thioketones adds 210 milliliters of trichloromethanes, filter, filtrate is washed with saturated sodium bicarbonate, washing, the organic phase anhydrous magnesium sulfate drying, filter, concentrated, obtain yellow solid 1 ', 3 ' dithio [4 ', 5 ': 5,6] [Isosorbide-5-Nitrae] two thiophene English [2,3-b] quinolyl-2-ketone also;
Step 2; under nitrogen protection; in the step 11 ' of gained; 3 '-dithio [4 '; 5 ': 5; 6] [1; 4] two thiophene English also [2; 3-b] drip the ethanolic soln of sodium hydroxide in quinolyl-2-ketone; 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 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 dropwise adds Nickel dichloride hexahydrate in the orange clear liquid; 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 add 0.5 mmole Nickel dichloride hexahydrate, per 0.5 mmole Nickel dichloride hexahydrate adds 10 milliliters of ethanol; reacted 2 hours; continue in the exposure air to stir 0.5 hour, solution becomes brown by purple, filters; the ethanolic soln that adds Tetrabutylammonium bromide in the filtrate; 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 add 1.5 mmole Tetrabutylammonium bromides, per 1.5 mmole Tetrabutylammonium bromides add 8 milliliters of ethanol; filter; obtain brown solid, be [Isosorbide-5-Nitrae] of the present invention two thiophene English also [2; 3-b] quinolyl-2, the 4-butyl ammonium of 3-disulfido nickel (III) title complex.
3. the application of complexes of nickel claimed in claim 1 in preparation near infrared accent Q dyestuff and laser protective material.
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| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148546A (en) * | 2006-09-22 | 2008-03-26 | 住友精化株式会社 | Light absorbing dyestuff composition |
| CN101610893A (en) * | 2007-01-17 | 2009-12-23 | 西巴控股有限公司 | Dithiolene metal complex colorless IR absorbers |
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|---|---|---|---|---|
| CN101148546A (en) * | 2006-09-22 | 2008-03-26 | 住友精化株式会社 | Light absorbing dyestuff composition |
| CN101610893A (en) * | 2007-01-17 | 2009-12-23 | 西巴控股有限公司 | Dithiolene metal complex colorless IR absorbers |
Non-Patent Citations (1)
| Title |
|---|
| 纪勇等.多硫二硫烯铜配合物:（n-Bu4N）[Cu（cddt）2] 和（Ph4P）[Cu（cddt）2]的合成、表征及其结构.《无机化学学报》.2002,第18卷(第11期),1123-1126. * |
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