CN104844638B - 4-sulfophthalic acid rare-earth metal complex, preparation method therefor and application thereof - Google Patents
4-sulfophthalic acid rare-earth metal complex, preparation method therefor and application thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- -1 4-sulfophthalic acid rare-earth metal Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 19
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- 230000005595 deprotonation Effects 0.000 claims description 9
- 238000010537 deprotonation reaction Methods 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 238000002050 diffraction method Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 238000005424 photoluminescence Methods 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000002411 thermogravimetry Methods 0.000 claims description 3
- 239000002198 insoluble material Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000010408 film Substances 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 3
- WNKQDGLSQUASME-UHFFFAOYSA-N 4-sulfophthalic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1C(O)=O WNKQDGLSQUASME-UHFFFAOYSA-N 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to a 4-sulfophthalic acid rare earth metal complex, a preparation method therefor and an application thereof. A general chemical formula of the 4-sulfophthalic acid rare earth metal complex is [Ln( H2O )2( SP )], wherein the Ln are plus trivalent lanthanide-series rare-earth ions Dy (III), Tb (III) and Er (III), and SP is a negative trivalent anion of the 4-sulfophthalic acid. The 4-sulfophthalic acid rare-earth metal complex is prepared by a solvent-thermal method which has a high yield, good reproducibility and high thermal stability. Under ultraviolet excitation, the solid-state complex can emit feature red light, green light or blue light, and has a high application value in the field of material science while being used as a photoluminescent material.
Description
With regard to subsidizing the statement of research or exploitation
The present patent application obtains state natural sciences fund (fund number: 21171129 and 21173157) and Tianjin height etc.
The subsidy of school's science and technology development fund planning item (fund number: 2012zd02).
Technical field
The present invention relates to metal-organic coordination polymer and its embedded photoluminescent material technical field, particularly joined by organic
The preparation method of the rare earth metal complex with two-dimensional layered structure and application that body 4- sulfosalicylic phthalate is constructed, its light
Learning property makes it can be applied in material science as embedded photoluminescent material.
Background technology
Rare earth organic fluorescent materials is because having monochromaticjty is good, excitation energy is low, luminous intensity is big, energy transfer efficiency is high etc.
Feature, has important application in luminous, the field such as hydrogen storage material, biomedicine, is increasingly paid close attention to by people, becomes and works as
One of more active field (c.-g. wang, y.-h. xing, z.- in front Rare Earth Functional Materials development and application research
p. li, j. li, x.-q. zeng, m.-f. ge, s.-y. niu,cryst. growth des. 2009,
9, 1525 ~ 1530; x.-d. guo, g.-s. zhu, f.-x. sun, z.-y. li, x.-j. zhao, x.-t.
li, h.-c. wang, s.-l. qiu,inorg.chem.2006, 45, 2581 ~ 2587).
Rare earth ion itselff-fTransition belongs to forbidden transition, and single rare earth ion is in visible and ultraviolet region table
Reveal very weak absorption.After the organic ligand of rare earth ion and high absorptivity forms metal complex, organic ligand can
By the Light energy transfer absorbing to rare earth ion, promote it to launch the characteristic fluorescence of rare earth ion and become important the lighting of a class
Material (Liu Hongmei, Jia Dandan, Song Aijun, Niu Shaoli, China rare earth journal, 2006,24 (supplementary issues): 10 ~ 15; h.-l.
huang, c.-f. zhong, h.-l. zhang, y. zhou,j lumin. 2008,128:1863 ~ 1866;
w.-t. chen, z.-l. yao,j coord chem. 2011, 64, 996 ~ 1005; f. t.
edelmann,coord. chem. rev. 2009, 253, 343; ~ 409; t. gunnlaugsson, a.
j. harte, j. p. leonard, m. n ieuwenhuyzen,chem. commun.2002, 2134 ~
2135; y. li, j.-w. yu, z.–y. liu, e.-c. yang, x.-j. zhao,inorg.chem.2015, 54, 153 ~ 160).In recent years, containβDiones, organic carboxyl acid class and crown ether, cave ether
Reported successively etc. the rare earth compounding of big ring class part and its structure and luminescent properties.Wherein, there is larger conjugation rigidity flat
The aromatic carboxylic acids class part in face has the good absorption coefficient of light in ultra-violet (UV) band, can be joined by the oxygen atom in carboxyl and rare earth ion
Position is formed has good stability, structure novelty, the rare earth luminescent material of excellent optical performance.Meanwhile, compared with other class parts,
The synthetically prepared relative ease of aromatic carboxylic acids class part, with more actual application value, is that the important rare earth luminescence of a class is quick
Change body (Guo Dongcai, Yi Liming, Shu Wangen, Zhang Zhenzhen, Zeng Zhaorong, Zhang Xiqian, spectroscopy and spectrum analysis, 2006,26
(11): 2003 ~ 2006;High match is ecological, Liu Xingwang, Wang Li, Shen Leijun, Jiang Jiadong, rare earth, 2010,31 (6): 17 ~
21).However, the preparation method of rare earth metal complex of phenyl many acids part and the correlative study in terms of luminescent properties
Still shallow, further investigate the structure of this metal complexes and the relation of luminescent properties, particularly the molecule of fluorescent chemicals is tied
Impact and the understanding to its rule that structure and surrounding environment are brought to compound spectra behavior and luminous intensity, seek for us
Look for the part of high absorptivity, synthesize new suitable rare earth metal complex, improve and improve rare-earth complexes luminous material
The aspect such as performance exist highly important meaning (Yang Bing, Li Ying, Xu Chuanxia, Xu Xianggang, Xie Minggui, chemical research with should
With 2003,15 (1): 11 ~ 16).
Content of the invention
Present invention aim at providing a class to have the 4- sulfosalicylic phthalate rare earth metal complex of two-dimensional layered structure
Thing and the preparation method and applications of such complex.Under ultraviolet light, such solid complex can be launched not
With the ruddiness of intensity, green glow or blue light, can have huge answering as embedded photoluminescent material in molecule base fluorescent material field
With being worth.
For achieving the above object, the following technology contents of present invention offer:
There is the 4- sulfosalicylic phthalate rare earth metal complex of following chemical general formulas: [ln (h2o)2(sp)], wherein ln
For positive trivalent La rear earth ion dy (iii), tb (iii) or er (iii)；Sp is that the negative trivalent of 4- sulfosalicylic phthalate is cloudy
Ion, its molecular formula is as follows:
The preparation method of 4- sulfosalicylic phthalate rare earth metal complex of the present invention it is characterised in that: by 4-
Sulfosalicylic phthalate and rare earth-iron-boron or rare earth oxide are in redistilled water and organic solvent via solvent thermal reaction
Obtain colourless or lightpink acicular crystal, the wherein mol ratio of 4- sulfosalicylic phthalate and rare earth-iron-boron or rare earth oxide
For 6.5: 3；Redistilled water: the volume ratio of organic solvent is 1.5 ~ 4: 1；Control the ph value scope of reaction system for 5 ~
6；At 170 ~ 200 DEG C, insulation dropped to room temperature after four days, was washed out, and is dried, obtains colourless or lightpink acicular crystal.
Solvent thermal reaction of the present invention refers in the stainless steel cauldron being lined with polytetrafluoroethylene (PTFE), with secondary steaming
Distilled water and organic solvent are reaction medium, make to produce inside container by temperature control oven heating (heated perimeter: 100 ~ 300 DEG C)
Spontaneous pressure (1 ~ 100 mpa) is so that indissoluble or insoluble material dissolve and crystallize precipitation under normal conditions.
Organic solvent of the present invention is methyl alcohol, ethanol, n, n- dimethylformamide or acetonitrile.Prioritizing selection water and first
Alcohol or ethanol composition mixed solvent.
The monocrystal of 4- sulfosalicylic phthalate rare earth metal complex of the present invention is it is characterised in that such coordinates
Thing crystallizes in triclinicpSpace group, cell parameter isa= 5.8993(5) ~ 5.9689(19) å,b= 9.3171
(8) ~ 9.414(3) å,c= 10.3925(9) ~ 10.437(3) å, α = 98.143(4) ~ 98.247(2)o,β= 94.1480(10) ~ 94.5020(10)o,107.776(2) ~ 107.9060(10)o,v= 534.22(8)
~ 547.8(3) å3,z= 2；It is shown in Table 1.Rare earth metal complex of the present invention, its elementary cell is two crystallography
Upper carboxyl of equal value, the rare earth ion of nine coordinations passes through a 4- sulfosalicylic phthalate trivalent anion deprotonation is assembled
Become a centrosymmetric double-core subelement, adjacent double-core subelement passes through the another one deprotonation of organic ligand further
Carboxyl and the sulfonic group of a deprotonation expand and form two-dimensional layer skeleton structure, its crystal structure is shown in Fig. 1.
The characteristic IR absorbance peaks of such rare earth compounding be 3421 ± 5 cm-1, 1542±3 cmˉ1, 1493±3 cm
ˉ1, 1440±2 cmˉ1, 1368±2 cmˉ1, 1233±3 cmˉ1, 1171 cmˉ1, 1078±4 cmˉ1, 1054 cm
ˉ1, 900±2 cmˉ1, 861±3 cmˉ1, 776±2 cmˉ1, 678±2 cmˉ1, 644±2 cmˉ1(see Fig. 2)；Should
Class complex has higher heat endurance, and its two-dimensional layer skeleton decomposes (see Fig. 3) afterwards at 513 DEG C.
The preparation method of rare earth metal complex monocrystal of the present invention is as follows:
By 4- sulfosalicylic phthalate and rare earth-iron-boron or rare earth oxide warp in redistilled water and organic solvent
Colourless or lightpink acicular crystal, wherein 4- sulfosalicylic phthalate and rare earth-iron-boron or rare earth oxygen are obtained by solvent thermal reaction
The mol ratio of compound is 6.5: 3；Redistilled water: the volume ratio of organic solvent is 1.5 ~ 4: 1；Control the ph of reaction system
Value scope is 5 ~ 6；At 170 ~ 200 DEG C, insulation dropped to room temperature after four days, was washed out, and is dried, obtains colourless or lightpink
Acicular crystal.
The present invention further discloses embedded photoluminescent material is being prepared by 4- sulfosalicylic phthalate rare earth metal complex
The application of aspect, wherein said embedded photoluminescent material refers to photoluminescence film, luminous energy conversion film for agriculture use or canopy film, sends out
Optical plastic or luminous paint etc..
The distinguishing feature of the 4- sulfosalicylic phthalate rare earth metal complex of present invention preparation is:
(1) present invention be by organic ligand 4- sulfosalicylic phthalate construct two-dimensional layer, there is fluorescent characteristic
Rare earth metal complex.
(2) the solid-state rare earth metal complex in the present invention adopt solvent thermal process prepare, yield is higher, favorable reproducibility,
There is higher heat endurance, can be applied in material science as embedded photoluminescent material.
Brief description
Fig. 1 complex [ln (h2o)2(sp) crystal structure figure (Fig. 1 a-b)]；
Fig. 2 complex [ln (h2o)2(sp) infrared spectrogram]；
Fig. 3 complex [ln (h2o)2(sp) thermogravimetric analysis figure]；
Fig. 4 complex [ln (h2o)2(sp) fluorescence spectra].
Specific embodiment
For purposes of simplicity and clarity, the hereafter appropriate description eliminating known technology, in order to avoid those are unnecessary
The description to the technical program for the details impact.Below in conjunction with preferred embodiment, the present invention will be further described, especially in addition
Illustrate, prepare initial substance 4- sulfosalicylic phthalate, hydrated rare-earth chloride or the rare-earth oxidation of the compounds of this invention
Thing all can be commercially.
Embodiment 1
The synthesis of 4- sulfosalicylic phthalate rare earth metal complex a:
By 4- sulfosalicylic phthalate (0.65 mM, 160.2 milligrams) and six chloride hydrate dysprosiums (0.3 mM,
113.1 milligrams) it is dissolved in redistilled water (8.0 ml) and the mixed solvent of methyl alcohol (2.0 ml).Adjust reaction with triethylamine
The ph of system is 6, after stirring several minutes, reactant mixture is encapsulated in 23.0 milliliters of water heating kettle.By the reaction after sealing
Kettle is transferred in temperature control oven, after being incubated four days at 170 DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature.Open
Directly obtain colourless acicular crystal after reactor, after methyl alcohol washing, obtain complex a in air drying.
Embodiment 2
The synthesis of 4- sulfosalicylic phthalate rare earth metal complex b:
By 4- sulfosalicylic phthalate (0.65 mM, 160.2 milligrams) and six chloride hydrate terbiums (0.3 mM,
112.0 milligrams) it is dissolved in redistilled water (6.0 ml) and the mixed solvent of ethanol (4.0 ml).Adjust reaction with triethylamine
The ph of system is 6, after stirring several minutes, reactant mixture is encapsulated in 23.0 milliliters of water heating kettle.By the reaction after sealing
Kettle is transferred in temperature control oven, after being incubated four days at 170 DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature.Open
Directly obtain colourless acicular crystal after reactor, after methyl alcohol washing, obtain complex b in air drying.
Embodiment 3
The synthesis of 4- sulfosalicylic phthalate rare earth metal complex c:
By 4- sulfosalicylic phthalate (0.65 mM, 160.2 milligrams) and erbium oxide (0.3 mM, 114.8 milligrams)
It is dissolved in redistilled water (8.0 ml) and the mixed solvent of ethanol (2.0 ml).With the ph that triethylamine adjusts reaction system it is
5, after stirring several minutes, reactant mixture is encapsulated in 23.0 milliliters of water heating kettle.Reactor after sealing is transferred to control
In warm baking oven, after being incubated four days at 200 DEG C, with 3.0 DEG C of h–1Rate program be cooled to room temperature.Open straight after reactor
Connect and obtain lightpink acicular crystal, after methyl alcohol washing, obtain complex c in air drying.
The structural characterization of the 4- sulfosalicylic phthalate rare earth metal complex (embodiment 1-3, a-c) of present invention preparation is such as
Under:
(1) complex crystal structure determination (Fig. 1)
Under an optical microscope, select the monocrystal being dimensioned for, in bruker apex ii under 296 k or 173 k
On ccd diffractometer, with through graphite monochromatised mo-k alpha ray (λ=0.71073), withMode collects diffraction data.
All diffraction datas carry out semiempirical absorption correction by sadabs software with multi-scan method.Cell parameter uses a young waiter in a wineshop or an inn
Multiplication determines.Data convert and structure elucidation are completed using saint and shelxl program bag respectively.The full square of all non-hydrogen atoms
Battle array least square method carries out anisotropy refine.The partial parameters of crystallography point diffraction Data Collection and structure refinement are shown in Table 1.As
Shown in Fig. 1, in such complex, in two crystallography, equivalence, the rare earth ions of nine coordinations are by 4- sulfo group O-phthalic
The carboxyl of one deprotonation of sour trivalent anion is gathered into a centrosymmetric double-core subelement, adjacent double-core subelement
The sulfonic group of the carboxyl of another one deprotonation and a deprotonation that pass through organic ligand further is expanded and is formed a two dimension
Layered framework structure.
Table 1. 4- sulfosalicylic phthalate rare earth metal complex
Predominant crystal data and refined parameters
(2) complex infrared spectrum measurement (Fig. 2)
The infrared spectrum of complex is surveyed on the infrared spectrometer of nicolet ft-ir-200 using pellet technique
Fixed, spectral scanning range be 4000-400 cm-1.Infrared test result (see Fig. 2) shows the infrared spy of such rare earth compounding
Levy absworption peak be 3421 ± 5 cm-1, 1542±3 cmˉ1, 1493±3 cmˉ1, 1440±2 cmˉ1, 1368±2 cmˉ1,
1233±3 cmˉ1, 1171 cmˉ1, 1078±4 cmˉ1, 1054 cmˉ1, 900±2 cmˉ1, 861±3 cmˉ1, 776
±2 cmˉ1, 678±2 cmˉ1, 644±2 cmˉ1.
(3) thermal analysis analysis measures (Fig. 3)
The thermogravimetric analysis experiment of complex is complete on the thermogravimetric analyzer of shimadzu simultaneous dtg 60a
Become, under nitrogen protection with the heating rate of 5 DEG C/min, complex sample is heated to 800 DEG C from room temperature.Measurement result (figure
3) show that the two-dimensional framework of such rare earth metal complex being capable of stable existence before 513 DEG C.After temperature continues to raise, join
The skeleton of compound starts to decompose, and residual residue is rare earth oxide.
Embodiment 4
(embodiment 1-3, a-c) rare earth metal complex optical property research of present invention preparation is as follows:
After the crystalline state complex solids enrichment obtained by embodiment 1-3, through grinding process further,
Jobin yvon (horiba) fluorolog-3 XRF carries out the test of solid fluorescence.Test result (see Fig. 4) table
Bright under ultraviolet excitation, complex sample a obtains stronger emission peak at 479,574 and 616 nm;Complex sample b
Obtain strong emission peak at 491,544,586 and 616 nm, complex sample c obtains relatively at 496,598 and 617 nm
Strong emission peak, that is, such complex can send the red, green, blue of feature.
Rare earth metal complex proposed by the present invention be a kind of can be senior glimmering with stable existence under normal temperature and pressure conditionses
Luminescent material, has that adjustable structure, preparation be simple, sensitized luminescence effect clear advantage, can be used to make photic solid glimmering
(such as photoluminescence film, luminous energy conversion film for agriculture use or canopy film, luminescent plastic or luminous paint etc. are expected to dividing luminescent material
Subbase fluorescence chemical field is applied.
Claims (6)
1.4- sulfosalicylic phthalate rare earth metal complex monocrystalline be used for embedded photoluminescent material aspect application it is characterised in that
Such complex crystal in anorthic system, space group isp, cell parameter isa= 5.8993(5) ~ 5.9689(19) å,b
= 9.3171(8) ~ 9.414(3) å,c= 10.3925(9) ~ 10.437(3) å,α= 98.143(4) ~
98.247(2)o,β= 94.1480(10) ~ 94.5020(10)o,γ= 107.776(2) ~ 107.9060(10)o,v= 534.22(8) ~ 547.8(3) å3,z= 2；In such complex, equivalence, nine coordinations dilute in two crystallography
The carboxyl of a deprotonation by 4- sulfosalicylic phthalate trivalent anion for the native ion is gathered into one centrosymmetric pair
Nucleon unit, adjacent double-core subelement is further by the carboxyl of another one deprotonation and a deprotonation of organic ligand
Sulfonic group expand formed a two-dimensional layer skeleton structure, its structure
[ln(h2o)2(sp)]；
Wherein ln is positive trivalent La rear earth ion, ln=dy (iii), tb (iii) or er (iii)；Sp is 4- sulfo group neighbour's benzene
The negative trivalent anion of dioctyl phthalate, its molecular formula is as follows:
.
2. the main infrared signature absorption peak of the application described in claim 1, wherein such complex monocrystal is 3421 ± 5 cm
ˉ1, 1542±3 cmˉ1, 1493±3 cmˉ1, 1440±2 cmˉ1, 1368±2 cmˉ1, 1233±3 cmˉ1, 1171
cmˉ1, 1078±4 cmˉ1, 1054 cmˉ1, 900±2 cmˉ1, 861±3 cmˉ1, 776±2 cmˉ1, 678±2 cm
ˉ1, 644±2 cmˉ1, there is infrared spectrogram as shown in Figure 2；The two-dimensional layer skeleton of complex can before 513 DEG C
Stable existence, has thermogravimetric analysis figure as shown in Figure 3.
3. the application described in claim 1, the preparation method of wherein this complex monocrystal is: by 4- sulfosalicylic phthalate and dilute
Native chloride or rare earth oxide obtain colourless or lightpink pin via solvent thermal reaction in redistilled water and organic solvent
Shape crystal, the wherein mol ratio of 4- sulfosalicylic phthalate and rare earth-iron-boron or rare earth oxide are 6.5: 3；Second distillation
Water: the volume ratio of organic solvent is 1.5 ~ 4: 1；The ph value scope controlling reaction system is 5 ~ 6；At 170 ~ 200 DEG C
Insulation dropped to room temperature after four days, was washed out, and is dried, obtains colourless or lightpink acicular crystal.
4. apply described in claim 3, the stainless steel that wherein said solvent thermal reaction refers in inner liner polytetrafluoroethylene is anti-
Answer in kettle, with redistilled water and organic solvent as reaction medium, heating 100 ~ 300 DEG C by temperature control oven makes inside container
Produce spontaneous 1 ~ 100 mpa pressure so that indissoluble or insoluble material dissolve and crystallize precipitation under normal conditions.
5. the application described in claim 4, wherein said organic solvent is methyl alcohol, ethanol, n, n- dimethylformamide, acetonitrile
One or more mixed solvents.
6. the application described in claim 1, embedded photoluminescent material therein refer to photoluminescence film, luminous energy conversion agricultural thin
Film or canopy film, luminescent plastic or luminous paint.
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