CN114181234A - Chiral ytterbium near-infrared luminescent eutectic material and preparation method thereof - Google Patents
Chiral ytterbium near-infrared luminescent eutectic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 238000003756 stirring Methods 0.000 claims abstract description 27
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- 239000013110 organic ligand Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
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- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- -1 methane anion Chemical class 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
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- 239000000047 product Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 abstract description 9
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- FHIAPLHUANFKGE-UHFFFAOYSA-N CC(C1=NC=CN=C1C1=NC=CC=C1)=O.I Chemical compound CC(C1=NC=CN=C1C1=NC=CC=C1)=O.I FHIAPLHUANFKGE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
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- DBZAKQWXICEWNW-UHFFFAOYSA-N 2-acetylpyrazine Chemical compound CC(=O)C1=CN=CC=N1 DBZAKQWXICEWNW-UHFFFAOYSA-N 0.000 description 2
- KMRMUZKLFIEVAO-UHFFFAOYSA-N 7,7-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1C2C(C)(C)C1CC=C2C=O KMRMUZKLFIEVAO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 description 2
- 238000001142 circular dichroism spectrum Methods 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 229920000742 Cotton Polymers 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 150000001216 Samarium Chemical class 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 150000001225 Ytterbium Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- 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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Abstract
The invention discloses a chiral ytterbium near-infrared luminescent eutectic material and a preparation method thereof, belonging to the technical field of rare earth functional materials. The chemical formula of the eutectic material is [ Yb (dbm) ]3L]‑[Yb(dbm)3C2H5OH]. The preparation method of the eutectic material comprises the following steps: will dissolve Yb (dbm)3(H2And O) adding the toluene solution into an ethanol solution dissolved with a chiral ligand L, stirring, filtering, putting the obtained solution into a test tube, putting the test tube in the atmosphere of normal hexane, obtaining light yellow crystals after 5-7 days, filtering, washing and drying to obtain the eutectic material. The eutectic material has excellent near-infrared luminescent performance, and has wide application prospect in the aspects of fluorescence immunoassay, optical amplifiers, optical fiber network communication, light conversion molecular devices and the like as a novel material.
Description
Technical Field
The invention belongs to the technical field of rare earth functional materials, and particularly relates to a chiral ytterbium near-infrared luminescent eutectic material and a preparation method thereof.
Background
Because the rare earth ions have unique f electron layer configuration and 4 f-4 f electron transition, the corresponding rare earth complex has characteristic luminescence property. Compared with europium, terbium and samarium complexes with visible light luminescent properties, the number of publicly reported rare earth near-infrared luminescent complexes is very limited. The rare earth ytterbium ion has near-infrared luminescence performance, is characterized in that the near-infrared luminescence wavelength is about 980nm, and has wide application prospect in the aspects of fluorescence immunoassay, optical amplification devices, optical fiber network communication and the like as a near-infrared luminescent material. However, the molar absorption coefficient of ytterbium ion is low, and the absorption capability of ytterbium ion to excitation light is weak, so that an organic compound with a large pi conjugated system is generally used as an 'antenna' ligand to absorb photons, and the effective energy transfer of light energy from the antenna ligand to the ytterbium ion is realized through a triplet state energy level, so that the emission of the ytterbium ion is sensitized, and the near-infrared luminescence of the ytterbium ion is realized. The beta-diketone organic ligand has a large pi conjugated molecular structure and a high molar absorption coefficient, can realize efficient energy transfer of photons, and particularly can further improve the luminous efficiency of materials due to the existence of a synergistic ligand, so that the rare earth complex based on the beta-diketone 'antenna' ligand has high luminous efficiency. In addition, the beta-diketone ligand also has an O, O-bidentate coordination mode, can chelate rare earth ions to form a stable complex, can emit light in a solid-liquid mode, and has wide application prospect. On the other hand, a eutectic is a multi-component crystalline material composed of two or more molecules of different structures in a certain ratio. Its outstanding advantage is to improve the physical and chemical properties of a single component constituting the eutectic molecule. At present, most of the reported eutectic molecular materials are composed of different organic molecules, such as drug molecular eutectic and energy material eutectic. The pure rare earth near-infrared luminescent complex eutectic is not reported in documents.
In addition, besides excellent luminescence properties, the chiral ytterbium beta-diketone complex may also show some interesting physical properties related to chirality, such as special properties of nonlinear optics (NLO), Circular Polarization Luminescence (CPL) and the like, and is a potential multifunctional material. At present, no article of chiral ytterbium beta-diketone complex eutectic is published, and no related patent is disclosed. Therefore, the prepared chiral ytterbium beta-diketone complex eutectic with excellent near-infrared luminescence property has theoretical research significance and practical application value.
Disclosure of Invention
Based on the chiral ytterbium near-infrared luminescent eutectic material and the preparation method thereof, the preparation method has the advantages of simple process, normal-temperature and normal-pressure reaction, easy post-treatment and high yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chiral ytterbium near-infrared luminescent eutectic material is provided, and the molecular formula of the chiral ytterbium near-infrared luminescent eutectic material is [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]Wherein dbm is dibenzoylmethane anion, L is a chiral mono-bidentate N-containing organic ligand of S configuration: (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine.
Preferably, the eutectic material is crystallized in monoclinic non-centrosymmetric space group P21The unit cell parameters are as follows:
α＝γ＝90°，β＝98.852°(6)，
Z＝2，Dc＝1.435g·cm–1，μ＝2.092mm–1，R1＝0.0543，wR2＝0.0847。
the invention provides a preparation method of a chiral ytterbium near-infrared luminescent eutectic material, which comprises the following steps:
put Yb (dbm)3(H2O) is dissolved in toluene and stirred for 5-10min to obtain Yb (dbm)3(H2O) in toluene;
dissolving the S-configuration chiral mono-bidentate N-containing organic ligand L in ethanol, and stirring for 5-10min to obtain an ethanol solution in which the L is dissolved;
③ Yb (dbm) obtained in the step (i)3(H2And O) adding the toluene solution into the ethanol solution dissolved with L obtained in the step II, continuously stirring for 25-30min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube in an n-hexane atmosphere, obtaining light yellow crystals after 5-7 days, filtering, washing with deionized water and ethanol in sequence, and drying at room temperature to obtain the chiral ytterbium near-infrared luminescent eutectic material.
Preferably, Yb (dbm) in the step (i)3(H2O) in toluene Yb (dbm)3(H2O) concentration is 0.008-0.02 mol/L.
Preferably, the concentration of L in the ethanol solution of the chiral mono-bidentate N-containing organic ligand L in the step (II) is 0.01-0.035 mol/L.
Preferably, Yb (dbm) in the step (i)3(H2The ratio of O) to the amount of L in step (II) is 1: 1.
Preferably, Yb (dbm) in the step (c)3(H2The volume ratio of the toluene solution of O) to the ethanol solution of L is (5-12) to (3-8).
Preferably, Yb (dbm) in the step (i)3(H2O) the preparation method is as follows: dissolving dibenzoyl methane (Hdbm) in acetonitrile, stirring for 15-20min to obtain acetonitrile solution of dibenzoyl methane, adding ammonia water, and dropwise adding Yb (CH) while stirring3COO)3·6H2O, stirring for 2 hr to complete reaction, filtering, washing the precipitate with small amount of deionized water, and vacuum drying to obtain light yellow product Y (dbm)3(H2O)。
Preferably, the mass-to-volume ratio of the dibenzoylmethane (Hdbm) to the acetonitrile is: 1.0g, 6 mL; the concentration of the ammonia water is 1 mol/L; the Yb (CH)3COO)3·6H2Yb (CH) in an aqueous solution of O3COO)3·6H2The concentration of O was 0.262 mol/L.
Preferably, the acetonitrile, ammonia and Yb (CH)3COO)3·6H2Water solubility of OThe volume ratio of the liquid is 4:3: 2.
The invention has the beneficial effects that:
(1) the invention adopts a chiral mono-bidentate N-containing organic ligand L: β -diketone precursor of (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine and rare earth ytterbium: yb (dbm)3(H2O) reacting to obtain the novel chiral ytterbium complex eutectic. The synthesis method has simple process, normal temperature and normal pressure reaction, and the obtained crystalline product is easy to separate and purify and has high yield.
(2) The chiral ytterbium beta-diketone complex eutectic prepared by the invention has excellent near-infrared luminescence property. The reason is that: (a) beta-diketone (dbm) triplet state with energy level higher than Yb3+The resonance energy level of the ion can effectively transfer the excitation light energy to Yb3+Ions; (b) due to the introduction of the chiral mono-bidentate N-containing cooperative ligand, the molecular structure of the compound presents non-central symmetry, and the non-central symmetry molecular structure is reported to be favorable for enhancing the luminescence property of the rare earth complex; (c) in particular, because of the formation of eutectic molecules, which are characterized by a significant improvement in the properties of the individual components that make up the eutectic molecules. In addition, chiral rare earth beta-diketone near-infrared luminescent eutectic materials are not reported, and the ytterbium beta-diketone complex eutectic claimed by the patent has excellent luminescent performance and chiral optical activity. Therefore, the invention also fills the blank of the material.
(3) The near-infrared luminescent material has the advantages of mild synthesis conditions, high yield, good stability and easy separation and purification, and is expected to have wide application prospects in the aspects of fluorescence immunoassay, optical amplifiers, optical fiber network communication, light conversion molecular devices and the like as a novel near-infrared luminescent material.
Drawings
FIG. 1 shows a chiral ytterbium near-IR luminescent eutectic material [ Yb (dbm) ] of example 23L]-[Yb(dbm)3C2H5OH]The molecular structure of (1), wherein the H atom is omitted.
FIG. 2 shows a chiral ytterbium near-IR luminescent eutectic material [ Yb (dbm) ]in example 23L]-[Yb(dbm)3C2H5OH]Medium Yb3+Coordination geometry of the ions.
FIG. 3 shows a chiral ytterbium near-IR luminescent eutectic material [ Yb (dbm) ]in example 33L]-[Yb(dbm)3C2H5OH]The emission spectrum of (2).
FIG. 4 shows a chiral ytterbium near-IR luminescent eutectic material [ Yb (dbm) ]in example 33L]-[Yb(dbm)3C2H5OH]The excitation spectrum of (1).
FIG. 5 shows a chiral ytterbium near-IR luminescent eutectic material [ Yb (dbm) ] of example 33L]-[Yb(dbm)3C2H5OH]The emission lifetime map of (1).
FIG. 6 shows a chiral ytterbium near-IR luminescent eutectic material [ Yb (dbm) ] of example 33L]-[Yb(dbm)3C2H5OH]Chiral circular dichroism spectra of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The preparation method of the S-configuration chiral mono-bidentate N-containing organic ligand L comprises the following steps:
(i) preparation of 2- (acetylpyrazinyl) pyridine iodide salt intermediate: 3.8g of 2-acetylpyrazine was added to a 250mL round bottom flask, dissolved in 10mL pyridine, and 15mL pyridine in which 12g iodine was dissolved was added to the round bottom flask, the mixture was heated to 120 ℃ and reacted for 4.5 hours, then cooled to room temperature and filtered, washed with pyridine, and dried under vacuum to give a brown solid, which was the desired intermediate, 2- (acetylpyrazinyl) pyridine iodonium salt.
(ii) Synthesis of chiral mono-and bidentate N-containing organic ligand L: 2.5g of the 2- (acetylpyrazinyl) pyridinium iodide salt intermediate prepared in step (i) and 3.0g ammonium acetate (NH) were weighed4Ac) was placed in a three-necked flask and added30mL of formamide (HCONH)2) Adding 2.0g of S-configuration myrtenal (+) -myrtenal under continuous stirring, heating to 85 ℃, stirring under nitrogen for reaction for 15 hours, cooling to room temperature overnight, filtering to obtain a light gray solid, recrystallizing by using a mixed solvent of ethyl acetate and methanol, and drying at room temperature to obtain the chiral mono-bidentate and N-containing organic ligand L, wherein the yield of the chiral mono-bidentate and N-containing organic ligand L is 81%. Elemental analysis: according to the formula C16H15N3(molecular weight 249.31): calculated value (%): c, 77.08; h, 6.06; n, 16.85; found (%): c, 76.83; h, 6.19; n, 16.57.
Example 1
A chiral ytterbium near-infrared luminescent eutectic material is provided, and the molecular formula of the chiral ytterbium near-infrared luminescent eutectic material is [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]Wherein dbm is dibenzoylmethane anion, L is a chiral mono-bidentate N-containing organic ligand of S configuration: (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine.
Wherein the eutectic material is crystallized in monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows:
α＝γ＝90°，β＝98.852°(6)，
Z＝2，Dc＝1.435g·cm–1，μ＝2.092mm–1，R1＝0.0543，wR2＝0.0847。
example 2
A preparation method of a chiral ytterbium near-infrared luminescent eutectic material comprises the following steps:
put Yb (dbm)3(H2O) is dissolved in 5 to 12mL of toluene and stirred for 5 to 10min to obtain Yb (dbm) with the concentration of (0.008 to 0.02mol/L)3(H2O) in toluene;
dissolving the S-configuration chiral mono-bidentate N-containing organic ligand L in 3-8mL of ethanol, and stirring for 5-10min to obtain an ethanol solution in which (0.01-0.035mol/L) L is dissolved;
③ mixing the obtained Yb (dbm)3(H2O) into the ethanol solution containing L obtained in the step (2), wherein Yb (dbm)3(H2And (3) the volume ratio of the toluene solution of O) to the ethanol solution of L is (5-12) to (3-8), stirring at room temperature for 25-30min, filtering, transferring the obtained clear solution into a test tube, placing the test tube in an n-hexane atmosphere for 5-7 days to obtain a light yellow crystal, filtering, washing with deionized water and ethanol in sequence, and drying at room temperature to obtain the chiral ytterbium near-infrared luminescent eutectic material.
In the above-mentioned embodiment, Yb (dbm)3(H2O) the preparation method is as follows:
the first method comprises the following steps: dibenzoyl methane (Hdbm) and acetonitrile in a mass to volume ratio: mixing 1.0g and 6mL, stirring for 15-20min to obtain acetonitrile solution of dibenzoyl methane, adding 1mol/L ammonia water into the acetonitrile solution, and dropwise adding Yb (CH) dissolved with 0.262mol/L while stirring continuously3COO)3·6H2O, generating precipitate, stirring for 2 hr to complete reaction, filtering, washing the precipitate with deionized water, and vacuum drying to obtain light yellow product Y (dbm)3(H2O), wherein Y (dbm)3(H2O) yield was 95% (calculated as Yb). Elemental analysis: according to the formula C45H35O7Yb (molecular weight 860.80): calculated value (%): c, 62.79; h, 4.10; found (%): c, 62.33; h, 4.21. Infrared Spectrum IR (KBr, cm)–1)：3325(b)，3021(w)，1609(s)，1527(m)，1336(s)，1228(m)，1138(m)。
And the second method comprises the following steps: yb (dbm)3(H2O) the specific preparation method is as follows:
dissolving 4.0g of dibenzoylmethane (Hdbm) in 24mL of acetonitrile, stirring for 15min to obtain an acetonitrile solution of dibenzoylmethane, adding 18mL of 1mol/L ammonia water to the acetonitrile solution, and dropwise adding 12mL of Yb (CH) dissolved with 1.44g of ammonia water while stirring3COO)3·6H2O in water solution, precipitate is generated, and stirring is continued for 2 hoursAllowing the reaction to complete, filtering, washing the precipitate with deionized water, and vacuum drying to obtain a light yellow product, Y (dbm)3(H2O) wherein Y (dbm)3(H2O) yield was 95% (calculated as Yb). Elemental analysis: according to the formula C45H35O7Yb (molecular weight 860.80): calculated value (%): c, 62.79; h, 4.10; found (%): c, 62.33; h, 4.21. Infrared Spectrum IR (KBr, cm)–1)：3325(b)，3021(w)，1609(s)，1527(m)，1336(s)，1228(m)，1138(m)。
And the third is that: yb (dbm)3(H2O) the specific preparation method is as follows:
dissolving 2.0g of dibenzoylmethane (Hdbm) in 12mL of acetonitrile and stirring for 15min to obtain an acetonitrile solution of dibenzoylmethane, adding 9mL of 1mol/L ammonia water to the acetonitrile solution, and dropwise adding 6mL of Yb (CH) dissolved with 0.72g of ammonia water while stirring3COO)3·6H2O, generating precipitate, stirring for 2 hr to complete reaction, filtering, washing the precipitate with deionized water, and vacuum drying to obtain light yellow product Y (dbm)3(H2O) wherein Y (dbm)3(H2O) yield was 95% (calculated as Yb). Elemental analysis: according to the formula C45H35O7Yb (molecular weight 860.80): calculated value (%): c, 62.79; h, 4.10; found (%): c, 62.33; h, 4.21. Infrared Spectrum IR (KBr, cm)–1)：3325(b)，3021(w)，1609(s)，1527(m)，1336(s)，1228(m)，1138(m)。
Chiral ytterbium near-infrared luminescent eutectic material Yb (dbm) is analyzed by a Perkin-Elmer-240C element analyzer3L]-[Yb(dbm)3C2H5OH]C, H and N content analysis was performed, according to formula C108H88N3O13Yb2(molecular weight 1981.89) calculated (%): c, 65.45; h, 4.48; n, 2.12; found (%): c, 65.27; h, 4.56; n, 2.33.
Measuring chiral ytterbium near-infrared luminescent eutectic material Yb (dbm) at normal temperature by using Bruker SMAR APEX II CCD diffractometer single crystal diffractometer3L]-[Yb(dbm)3C2H5OH]The molecular structure of (1) is shown in figure 1, and it can be seen from the figure that the chiral near infrared luminescent material is composed of two different molecules Yb (dbm)3L and Yb (dbm)3C2H5OH co-crystallization forms. Yb (dbm)3Yb in L3+The ion is octadentate, forming YbO with six O atoms from three beta-diketone anions (dbm) and two N atoms provided by a chiral monodentate N-containing ligand L6N2A distorted inverted rectangular pyramid geometry as shown in figure 2 (a); yb (dbm)3C2H5Yb in OH3+The ion is heptadentate, forming YbO with six O atoms from three beta-diketone anions (dbm) and one O atom provided by ethanol as a coordinated solvent molecule7The geometrical configuration of the single-cap triangular pyramid is shown in the figure 2 (b).
Example 3
Chiral ytterbium near-infrared luminescent eutectic material [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]The preparation method comprises the following steps:
combining 86mg Yb (dbm)3(H2O) was dissolved in 5mL of toluene and stirred for 10min to obtain Yb (dbm)3(H2O) in toluene;
dissolving 25mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 3mL of ethanol, and stirring for 10min to obtain an L ethanol solution;
③ 5mL Yb (dbm)3(H2O) (0.1mmol) is added into 3mL of ethanol solution dissolved with chiral mono-bidentate and N-containing organic ligand L ((+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine (0.1mmol), stirred for 25min, filtered, the obtained clear solution is transferred into a test tube and placed in normal hexane atmosphere for natural diffusion, after 5 days, light yellow crystals are obtained, filtered, washed by 3mL of deionized water and 3mL of ethanol in sequence, and dried at room temperature, so that the chiral ytterbium near infrared luminescent eutectic material is prepared, and the yield is 91% (calculated according to Yb).
The chiral ytterbium near-infrared luminescent eutectic material in example 4 was tested for emission, excitation and luminescence using an FLS980P fluorescence spectrometer at room temperatureThe optical lifetimes are shown in fig. 3, 4, and 5, respectively. The test result shows that: chiral ytterbium eutectic material [ Yb (dbm)3L]-[Yb(dbm)3C2H5OH]When excited by 410nm of visible light, as shown in FIG. 4, it can emit Yb centered at 978nm3+The characteristic near infrared spectrum is shown in figure 3; through calculation and fitting, as shown in fig. 5, the luminescent lifetime of the near-infrared luminescence of the chiral ytterbium eutectic material is as high as 16.68 μ s, while most of the reported ytterbium near-infrared luminescent complexes require ultraviolet light for excitation, and the luminescent lifetime is usually less than 10 μ s. It can be seen that the disclosed chiral ytterbium eutectic material [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]Has longer luminescence decay life and excellent near-infrared luminescence property.
The chiral ytterbium eutectic material [ Yb (dbm) ] was tested using a Biologic MS-500Spectropolarimeter3L]-[Yb(dbm)3C2H5OH]The solid state circular dichroism spectrum of (a) is shown in fig. 6, and it can be seen from the figure that the eutectic material shows a positive Cotton effect at the wavelength λ of 330 and 418nm, confirming the chiral optical activity of the luminescent material.
Example 4
Chiral ytterbium near-infrared luminescent eutectic material [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]The preparation method comprises the following steps:
put 68.8mg Yb (dbm)3(H2O) was dissolved in 8mL of toluene and stirred for 8min to obtain Yb (dbm)3(H2O) in toluene;
dissolving 20mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 4mL of ethanol, and stirring for 8min to obtain an L ethanol solution;
③ will 8mL Yb (dbm)3(H2O) (0.08mmol) of toluene solution is added into 4mL of ethanol solution dissolved with chiral mono-bidentate and N-containing organic ligand L ((+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine (0.08mmol), stirred for 25min, filtered, the obtained clear solution is transferred into a test tube and placed in an N-hexane atmosphere for natural diffusion, a light yellow crystal is obtained after 6 days, filtered, washed by 3mL of deionized water and 3mL of ethanol in sequence,drying at room temperature to obtain the chiral ytterbium near-infrared luminescent eutectic material with the yield of 91% (calculated according to Yb).
Example 5
Chiral ytterbium near-infrared luminescent eutectic material [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]The preparation method comprises the following steps:
combining 77.4mg Yb (dbm)3(H2O) was dissolved in 10mL of toluene and stirred for 5min to obtain Yb (dbm)3(H2O) in toluene;
dissolving 22.5mg of S-configuration chiral mono-bidentate N-containing organic ligand L prepared by the method in 6mL of ethanol, and stirring for 5min to obtain an L ethanol solution;
③ to mix 10mL Yb (dbm)3(H2O) (0.09mmol) is added into 6mL of ethanol solution dissolved with chiral mono-bidentate and N-containing organic ligand L ((+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine (0.09mmol), stirred for 30min, filtered, the obtained clear solution is transferred into a test tube and placed in normal hexane atmosphere for natural diffusion, after 7 days, light yellow crystals are obtained, filtered, washed by 3mL of deionized water and 3mL of ethanol in sequence, and dried at room temperature, so that the chiral ytterbium near infrared luminescent eutectic material is prepared, and the yield is 91% (calculated according to Yb).
The chiral ytterbium near-infrared luminescent eutectic material and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A chiral ytterbium near-infrared luminescent eutectic material is characterized in that: the molecular formula of the chiral ytterbium near-infrared luminescent eutectic material is [ Yb (dbm) ]3L]-[Yb(dbm)3C2H5OH]Wherein dbm is diphenylmethyleneAcyl methane anion, L is a chiral mono-bidentate N-containing organic ligand of S configuration: (+) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine.
2. The chiral ytterbium near-infrared luminescent eutectic material of claim 1, wherein: the eutectic material is crystallized in monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows:
α＝γ＝90°，β＝98.852°(6)，
Z＝2，Dc＝1.435g·cm–1，μ＝2.092mm–1，R1＝0.0543，wR2＝0.0847。
3. a preparation method of a chiral ytterbium near-infrared luminescent eutectic material is characterized by comprising the following steps: the method comprises the following steps:
put Yb (dbm)3(H2O) is dissolved in toluene and stirred for 5-10min to obtain Yb (dbm)3(H2O) in toluene;
dissolving the S-configuration chiral mono-bidentate N-containing organic ligand L in ethanol, and stirring for 5-10min to obtain an ethanol solution in which the L is dissolved;
③ Yb (dbm) obtained in the step (i)3(H2Adding the toluene solution of O) into the ethanol solution dissolved with L obtained in the step II, continuously stirring for 25-30min at room temperature, filtering, transferring the obtained clear solution into a test tube, placing the test tube in an n-hexane atmosphere, obtaining light yellow crystals after 5-7 days, filtering, washing with deionized water and ethanol in sequence, and drying at room temperature to obtain chiral ytterbium near-redAn exo-luminescent eutectic material.
4. The method for preparing the chiral ytterbium near-infrared luminescent eutectic material, according to claim 3, characterized in that: in the step (I), Yb (dbm)3(H2O) in toluene Yb (dbm)3(H2O) concentration is 0.008-0.02 mol/L.
5. The method for preparing the chiral ytterbium near-infrared luminescent eutectic material, according to claim 3, characterized in that: in the step (II), the concentration of L in the chiral mono-bidentate N-containing organic ligand L ethanol solution is 0.01-0.035 mol/L.
6. The method for preparing the chiral ytterbium near-infrared luminescent eutectic material, according to claim 3, characterized in that: in the step (I), Yb (dbm)3(H2The ratio of O) to the amount of L in step (II) is 1: 1.
7. The method for preparing the chiral ytterbium near-infrared luminescent eutectic material, according to claim 3, characterized in that: said step (c) Yb (dbm)3(H2The volume ratio of the toluene solution of O) to the ethanol solution of L is (5-12) to (3-8).
8. The method for preparing the chiral ytterbium near-infrared luminescent eutectic material, according to claim 3, characterized in that: in the step (I), Yb (dbm)3(H2O) the preparation method is as follows: dissolving dibenzoyl methane (Hdbm) in acetonitrile, stirring for 15-20min to obtain acetonitrile solution of dibenzoyl methane, adding ammonia water, and dropwise adding Yb (CH) while stirring3COO)3·6H2O, stirring for 2 hr to complete reaction, filtering, washing the precipitate with small amount of deionized water, and vacuum drying to obtain light yellow product Y (dbm)3(H2O)。
9. The chiral ytterbium near-infrared of claim 8The preparation method of the luminescent eutectic material is characterized by comprising the following steps: the mass volume ratio of the dibenzoyl methane (Hdbm) to the acetonitrile is as follows: 1.0g, 6 mL; the concentration of the ammonia water is 1 mol/L; the Yb (CH)3COO)3·6H2Yb (CH) in an aqueous solution of O3COO)3·6H2The concentration of O was 0.262 mol/L.
10. The method for preparing the chiral ytterbium near-infrared luminescent eutectic material, according to claim 8, characterized in that: acetonitrile, ammonia water and Yb (CH)3COO)3·6H2The volume ratio of the aqueous solution of O is 4:3: 2.
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