CN114181234B - Chiral ytterbium near-infrared luminous eutectic material and preparation method thereof - Google Patents
Chiral ytterbium near-infrared luminous eutectic material and preparation method thereof Download PDFInfo
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- CN114181234B CN114181234B CN202111476398.2A CN202111476398A CN114181234B CN 114181234 B CN114181234 B CN 114181234B CN 202111476398 A CN202111476398 A CN 202111476398A CN 114181234 B CN114181234 B CN 114181234B
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- 230000005496 eutectics Effects 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 64
- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 57
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000004020 luminiscence type Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 50
- 239000013110 organic ligand Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 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 dibenzoylmethane anion Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 10
- 208000006637 fused teeth Diseases 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 abstract description 9
- 239000003446 ligand Substances 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000004891 communication Methods 0.000 abstract description 3
- 238000003018 immunoassay Methods 0.000 abstract description 3
- 239000013307 optical fiber Substances 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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
- 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
- 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 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003216 pyrazines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MQXKQIVXDZZYKX-UHFFFAOYSA-N 1-(3-pyridin-2-ylpyrazin-2-yl)ethanone Chemical compound CC(=O)c1nccnc1-c1ccccn1 MQXKQIVXDZZYKX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 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
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 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
- 238000005303 weighing Methods 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
-
- 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
- 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
-
- 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 discloses a chiral ytterbium near-infrared luminous 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) 3 L]‑[Yb(dbm) 3 C 2 H 5 OH]. The preparation method of the eutectic material comprises the following steps: yb (dbm) is dissolved in the mixture 3 (H 2 Adding the toluene solution of O) into ethanol solution dissolved with chiral ligand L, stirring, filtering, placing the obtained solution into a test tube, placing in an atmosphere of normal hexane for 5-7 days to obtain light yellow crystals, filtering, washing and drying to obtain the eutectic material. The eutectic material has excellent near infrared luminescence performance, and has wide application prospect in fluorescent immunoassay, optical amplifier, 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 ion has a unique f electron layer configuration, 4f-4f electron transition exists, and the corresponding rare earth complex has characteristic luminescence performance. Compared with europium, terbium and samarium complexes with visible light luminescence property, the quantity of the rare earth near infrared luminescence complexes disclosed and reported is very limited. The rare earth ytterbium ion has near infrared luminescence property, and is characterized in that the near infrared luminescence wavelength is about 980nm, and the rare earth ytterbium ion has wide application prospect in the aspects of fluorescence immunoassay, an optical amplifying device, optical fiber network communication and the like as a near infrared luminescent material. However, the molar absorption coefficient of ytterbium ions is low, the absorption capacity of excitation light is weak, and 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 ytterbium ions is realized through a triplet energy level, so that the emission of ytterbium ions is sensitized, and the near infrared luminescence of the ytterbium ions is realized. The beta-diketone organic ligand has a large pi conjugated molecular structure, has high molar absorption coefficient, can realize high-efficiency energy transfer of photons, and especially can further improve the luminous efficiency of the material by the existence of the 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-double-tooth coordination mode, can chelate rare earth ions to form a stable complex, can emit light in two solid-liquid forms, and has wide application prospect. On the other hand, a eutectic is a multicomponent crystalline material composed of two or more molecules of different structures in a certain proportion. The outstanding advantage is that it can improve the physical and chemical properties of a single component that makes up the eutectic molecule. Currently, the most reported eutectic molecular materials are composed of different organic molecules, such as drug molecule eutectic and energy material eutectic. Pure rare earth near infrared luminescent complex eutectic is not reported in the literature.
In addition, the chiral ytterbium beta-diketone complex has excellent luminescence performance, and may also show some interesting physical properties related to chirality, such as nonlinear optics (NLO), circular Polarized Luminescence (CPL) and other special properties, so that the chiral ytterbium beta-diketone complex 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 preparation of the chiral ytterbium beta-diketone complex eutectic with excellent near infrared luminescence performance has theoretical research significance and practical application value.
Disclosure of Invention
Based on the above, the invention provides the chiral ytterbium near-infrared luminescent eutectic material and the preparation method thereof, and 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 above purpose, the present invention adopts the following technical scheme:
a chiral ytterbium near-infrared luminous eutectic material has a molecular formula of [ Yb (dbm) ] 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Wherein dbm is dibenzoylmethane anion and L is a chiral mono-bidentate N-containing organic ligand of S configuration: (+) -2- (4 ',5' -pinene pyridinyl-2 ') pyrazines.
Preferably, the eutectic material is crystallized in a monoclinic system non-centrosymmetric space group P2 1 The unit cell parameters are as follows:α＝γ＝90°，β＝98.852°(6)，/>Z＝2，D c ＝1.435g·cm –1 ，μ＝2.092mm –1 ，R 1 ＝0.0543，wR 2 ＝0.0847。
the invention provides a preparation method of a chiral ytterbium near infrared light-emitting eutectic material, which comprises the following steps:
(1) yb (dbm) 3 (H 2 O) is dissolved in toluene and stirred for 5-10min to obtain Yb (dbm) 3 (H 2 O) toluene solution;
(2) dissolving chiral single-double-tooth N-containing organic ligand L in S configuration in ethanol, and stirring for 5-10min to obtain ethanol solution dissolved with L;
(3) the Yb (dbm) obtained in the step (1) is reacted with 3 (H 2 Adding the toluene solution of O) into the ethanol solution dissolved with L obtained in the step (2), continuously stirring at room temperature for 25-30min, filtering, transferring the obtained clear solution into a test tube, placing the test tube in the atmosphere of normal hexane for 5-7 days to obtain light yellow crystals, 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, in the step (1)Yb(dbm) 3 (H 2 Yb (dbm) in toluene solution of O) 3 (H 2 The concentration of O) is 0.008-0.02mol/L.
Preferably, the concentration of L in the ethanol solution containing the chiral monodentate N-containing organic ligand L in the step (2) is 0.01-0.035mol/L.
Preferably, yb (dbm) in the step (1) 3 (H 2 The ratio of O) to the amount of L material in step (2) is 1:1.
Preferably, yb (dbm) in the step (3) 3 (H 2 The volume ratio of the toluene solution of O) to the ethanol solution of L is (5-12): 3-8.
Preferably, yb (dbm) in the step (1) 3 (H 2 The preparation method of O) is as follows: dissolving dibenzoylmethane (Hdbm) in acetonitrile, stirring for 15-20min to obtain acetonitrile solution of dibenzoylmethane, adding ammonia water into the acetonitrile solution, and dropwise adding Yb (CH) under continuous stirring 3 COO) 3 ·6H 2 O aqueous solution, precipitate, stirring for 2 hr to complete reaction, filtering, washing precipitate with small amount of deionized water, and vacuum drying to obtain yellowish product, Y (dbm) 3 (H 2 O)。
Preferably, the mass-to-volume ratio of dibenzoylmethane (Hdbm) to acetonitrile is: 1.0 g/6 mL; the concentration of the ammonia water is 1mol/L; the Yb (CH) 3 COO) 3 ·6H 2 Yb (CH) in aqueous O solution 3 COO) 3 ·6H 2 The concentration of O was 0.262mol/L.
Preferably, the acetonitrile, ammonia and Yb (CH 3 COO) 3 ·6H 2 The volume ratio of the aqueous solution of O is 4:3:2.
The invention has the beneficial effects that:
(1) The invention adopts a chiral single-double tooth N-containing organic ligand L: β -diketone precursor of (+) -2- (4 ',5' -pinene pyridinyl-2 ') pyrazine with rare earth ytterbium: yb (dbm) 3 (H 2 O) 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 performance. The reason is that: (a) The energy level of the beta-diketone (dbm) triplet state is higher than Yb 3+ The resonance energy level of the ions can effectively transfer the excitation light energy to Yb 3+ Ions; (b) The molecular structure of the compound presents non-central symmetry due to the introduction of the chiral single-double-tooth N-containing synergistic ligand, and the non-central symmetry molecular structure is reported to be favorable for enhancing the luminous performance of the rare earth complex; (c) Particularly, due to the formation of eutectic molecules, the outstanding feature of the eutectic molecules is that the properties of the individual components constituting the eutectic molecules can be significantly improved. In addition, the chiral rare earth beta-diketone near infrared luminescence eutectic material is not reported yet, but the ytterbium beta-diketone complex eutectic material disclosed by the patent not only has excellent luminescence property, but also has chiral optical activity. Therefore, the invention fills the blank of the material.
(3) The near infrared luminescent material has mild synthesis conditions, high yield, good stability and easy separation and purification, and is expected to have wide application prospects as a novel near infrared luminescent material in the aspects of fluorescence immunoassay, optical amplifiers, optical fiber network communication, light conversion molecular devices and the like.
Drawings
FIG. 1 is a diagram of example 2 chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]The H atoms have been omitted.
FIG. 2 is a diagram of a chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) ] of example 2 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Middle Yb 3+ Coordination geometry diagram of ions.
FIG. 3 is a diagram of example 3 chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Is a graph of the emission spectrum of (a).
FIG. 4 is a diagram of example 3 chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Is a graph of the excitation spectrum of (a).
FIG. 5 is a diagram of example 3 chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Is a graph of the light emission lifetime of (a).
FIG. 6 is a diagram of example 3 chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Chiral circular dichroism spectrum of (3).
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
The preparation method of the chiral single-bidentate N-containing organic ligand L with the S configuration comprises the following steps:
(i) Preparation of 2- (acetylpyrazinyl) pyridinium iodide intermediate: into a 250mL round bottom flask, 3.8g of 2-acetylpyrazine was added, and 10mL of pyridine solution was used for dissolution, and 15mL of pyridine solution in which 12g of iodine was dissolved was added into the round bottom flask, and the mixture was heated to 120 ℃ for reaction for 4.5 hours, then cooled to room temperature and filtered, rinsed with pyridine, and dried under vacuum to obtain a brown solid, thus obtaining the desired intermediate 2- (acetylpyrazinyl) pyridine iodosalt.
(ii) Synthesis of chiral mono-bidentate N-containing organic ligand L: weighing 2.5g of the 2- (acetylpyrazinyl) pyridine iodonium salt intermediate prepared in step (i) and 3.0g of ammonium acetate (NH) 4 Ac) was placed in a three-necked flask and a further 30mL of formamide (HCONH) was added 2 ) 2.0g of S-configuration myrtenal (+) -myrtenal is added under continuous stirring, heated to 85 ℃, stirred under nitrogen for reaction for 15 hours, cooled to room temperature overnight, filtered to obtain light gray solid, recrystallized by a mixed solvent of ethyl acetate and methanol and dried at room temperature to obtain chiral mono-bidentate N-containing organic ligand L, wherein the yield of the chiral mono-bidentate N-containing organic ligand L is 81%. Elemental analysis: according to formula C 16 H 15 N 3 (molecular weight 249.31): calculated value (%): c,77.08; h,6.06; n,16.85; measured value (%): c (C),76.83；H,6.19；N,16.57。
Example 1
A chiral ytterbium near-infrared luminous eutectic material has a molecular formula of [ Yb (dbm) ] 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Wherein dbm is dibenzoylmethane anion and L is a chiral mono-bidentate N-containing organic ligand of S configuration: (+) -2- (4 ',5' -pinene pyridinyl-2 ') pyrazines.
Wherein the eutectic material is crystallized in a monoclinic system non-centrosymmetric space group P2 1 The unit cell parameters are as follows:α＝γ＝90°，β＝98.852°(6)，/>Z＝2，D c ＝1.435g·cm –1 ，μ＝2.092mm –1 ，R 1 ＝0.0543，wR 2 ＝0.0847。
example 2
A preparation method of a chiral ytterbium near-infrared luminescent eutectic material comprises the following steps:
(1) yb (dbm) 3 (H 2 O) was dissolved in 5-12mL of toluene and stirred for 5-10min to give Yb (dbm) at a concentration of (0.008-0.02 mol/L) 3 (H 2 O) toluene solution;
(2) dissolving the chiral single-double-tooth N-containing organic ligand L with the S configuration prepared by the invention in 3-8mL of ethanol, and stirring for 5-10min to obtain ethanol solution in which (0.01-0.035 mol/L) L is dissolved;
(3) mixing the Yb (dbm) obtained in step (1) 3 (H 2 O) into the ethanol solution dissolved with L obtained in the step (2), wherein Yb (dbm) 3 (H 2 The volume ratio of toluene solution of O) to ethanol solution of L is (5-12) (3-8), stirring at room temperature for 25-30min, filtering, transferring the obtained clear solution into test tube, placing the test tube in n-hexane atmosphere for 5-7 days to obtain pale yellow crystal, filtering, sequentially adding deionized water and ethyl acetateWashing with alcohol, and drying at room temperature to obtain the chiral ytterbium near infrared luminescent eutectic material.
In the above examples, yb (dbm) 3 (H 2 The preparation method of O) is as follows:
first kind: dibenzoylmethane (Hdbm) and acetonitrile are mixed according to the mass volume ratio: 1.0 g/6 mL of acetonitrile solution of dibenzoylmethane is obtained by mixing and stirring for 15-20min, 1mol/L of ammonia water is added into the acetonitrile solution, and 0.262mol/L of Yb (CH) is added dropwise under continuous stirring 3 COO) 3 ·6H 2 O aqueous solution, precipitate, stirring for 2 hr to complete reaction, filtering, washing precipitate with deionized water, and vacuum drying to obtain yellowish product, and obtaining Y (dbm) 3 (H 2 O), wherein Y (dbm) 3 (H 2 O) yield was 95% (calculated as Yb). Elemental analysis: according to formula C 45 H 35 O 7 Yb (molecular weight 860.80): calculated value (%): c,62.79; h,4.10; measured value (%): c,62.33; h,4.21. IR spectrum (KBr, cm) –1 )：3325(b)，3021(w)，1609(s)，1527(m)，1336(s)，1228(m)，1138(m)。
Second kind: yb (dbm) 3 (H 2 The specific preparation method of O) is as follows:
4.0g of dibenzoylmethane (Hdbm) was dissolved in 24mL of acetonitrile and stirred for 15 minutes to obtain an acetonitrile solution of dibenzoylmethane, 18mL of 1mol/L aqueous ammonia was added to the acetonitrile solution, and 12mL of Yb (CH) in which 1.44g was dissolved was further added dropwise with continuous stirring 3 COO) 3 ·6H 2 O aqueous solution, precipitate, stirring for 2 hr to complete reaction, filtering, washing precipitate with deionized water, and vacuum drying to obtain yellowish product, and obtaining Y (dbm) 3 (H 2 O) wherein Y (dbm) 3 (H 2 O) yield was 95% (calculated as Yb). Elemental analysis: according to formula C 45 H 35 O 7 Yb (molecular weight 860.80): calculated value (%): c,62.79; h,4.10; measured value (%): c,62.33; h,4.21. IR spectrum (KBr, cm) –1 )：3325(b)，3021(w)，1609(s)，1527(m)，1336(s)，1228(m)，1138(m)。
Third kind: y is Yb(dbm) 3 (H 2 The specific preparation method of O) is as follows:
2.0g of dibenzoylmethane (Hdbm) was dissolved in 12mL of acetonitrile and stirred for 15 minutes to obtain an acetonitrile solution of dibenzoylmethane, 9mL of 1mol/L aqueous ammonia was added to the acetonitrile solution, and 6mL of Yb (CH) in which 0.72g was dissolved was further added dropwise with continuous stirring 3 COO) 3 ·6H 2 O aqueous solution, precipitate, stirring for 2 hr to complete reaction, filtering, washing precipitate with deionized water, and vacuum drying to obtain yellowish product, and obtaining Y (dbm) 3 (H 2 O) wherein Y (dbm) 3 (H 2 O) yield was 95% (calculated as Yb). Elemental analysis: according to formula C 45 H 35 O 7 Yb (molecular weight 860.80): calculated value (%): c,62.79; h,4.10; measured value (%): c,62.33; h,4.21. IR spectrum (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) using Perkin-Elmer-240C elemental analyzer 3 L]-[Yb(dbm) 3 C 2 H 5 OH]C, H and N content analysis was performed according to formula C 108 H 88 N 3 O 13 Yb 2 (molecular weight 1981.89) calculated (%): c,65.45; h,4.48; n,2.12; measured value (%): c,65.27; h,4.56; n,2.33.
Chiral ytterbium near infrared luminescence eutectic material [ Yb (dbm) is measured at normal temperature by adopting Bruker SMAR APEX II CCD diffractometer single crystal diffractometer 3 L]-[Yb(dbm) 3 C 2 H 5 OH]The molecular structure of (2) is shown in FIG. 1, and it can be seen from the figure that the chiral near-infrared luminescent material consists of two different molecules Yb (dbm) 3 L and Yb (dbm) 3 C 2 H 5 OH co-crystals are formed. Yb (dbm) 3 Yb in L 3+ The ion is octacoordinate and forms YbO with six O atoms from three beta-diketone anions (dbm) and two N atoms provided by a chiral mono-bidentate N-containing ligand L 6 N 2 A twisted inverted rectangular pyramid geometry, the geometry of which is shown in figure 2 (a); yb (dbm) 3 C 2 H 5 Yb in OH 3+ The ion is heptacoordinated and forms YbO with six O atoms from three beta-diketone anions (dbm) and one O atom provided by one coordinated solvent molecule ethanol 7 The geometry of the single-cap triangular pyramid is shown in fig. 2 (b).
Example 3
Chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]The preparation method of (2) is as follows:
(1) 86mg Yb (dbm) 3 (H 2 O) was dissolved in 5mL of toluene and stirred for 10min to give Yb (dbm) 3 (H 2 O) toluene solution;
(2) dissolving 25mg of S-configuration chiral single-double-tooth N-containing organic ligand L prepared by the method in 3mL of ethanol, and stirring for 10min to obtain an ethanol solution of L;
(3) 5mL Yb (dbm) 3 (H 2 O) (0.1 mmol) was added to 3mL of an ethanol solution containing N-containing organic ligand L (+) -2- (4 ',5' -pinene pyridyl-2 ') pyrazine (0.1 mmol) dissolved therein, stirred for 25min, filtered, and the resulting clear solution was transferred into a test tube and placed in an atmosphere of N-hexane for natural diffusion to obtain pale yellow crystals after 5 days, and the pale yellow crystals were filtered, washed sequentially with 3mL of deionized water and 3mL of ethanol, and dried at room temperature to obtain a chiral ytterbium near infrared light emitting eutectic material with a yield of 91% (calculated as Yb).
The emission, excitation and luminescence lifetimes of the chiral ytterbium near infrared luminescence eutectic material of example 4 were tested at normal temperature using FLS980P fluorescence spectrometer, as shown in fig. 3, 4 and 5, respectively. The test results show that: chiral ytterbium eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]As shown in FIG. 4, under the excitation of 410nm visible light, yb with the center at 978nm can be emitted 3+ The characteristic near infrared spectrum is shown in figure 3; by calculation fitting, as shown in fig. 5, the luminescence lifetime of the chiral ytterbium eutectic material near-infrared luminescence is as high as 16.68 μs, while most of the reported ytterbium near-infrared luminescence complexes need ultraviolet excitation, and the luminescence lifetime is usually less than 10 μs. It can be seen that this patent publicationOpen chiral ytterbium eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Has longer luminescence decay life and excellent near infrared luminescence property.
Testing the chiral ytterbium eutectic material [ Yb (dbm) using a biologicc MS-500 electropolarimeter 3 L]-[Yb(dbm) 3 C 2 H 5 OH]As shown in fig. 6, it can be seen that the eutectic material shows positive Cotton effect at wavelengths λ=330 and 418nm, confirming the chiral optical activity of the luminescent material.
Example 4
Chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]The preparation method of (2) is as follows:
(1) 68.8mg Yb (dbm) 3 (H 2 O) was dissolved in 8mL of toluene and stirred for 8min to give Yb (dbm) 3 (H 2 O) toluene solution;
(2) dissolving 20mg of S-configuration chiral single-double-tooth N-containing organic ligand L prepared by the method in 4mL of ethanol, and stirring for 8min to obtain an ethanol solution of L;
(3) 8mL Yb (dbm) 3 (H 2 O) (0.08 mmol) was added to 4mL of an ethanol solution containing N-containing organic ligand L (+) -2- (4 ',5' -pinene pyridyl-2 ') pyrazine (0.08 mmol) dissolved in chiral monodentate, stirred for 25min, filtered, the resulting clear solution was transferred into a test tube, and placed in an atmosphere of N-hexane for natural diffusion, after 6 days, pale yellow crystals were obtained, filtered, washed with 3mL of deionized water and 3mL of ethanol in sequence, and dried at room temperature to obtain a chiral ytterbium near infrared light emitting eutectic material with a yield of 91% (calculated as Yb).
Example 5
Chiral ytterbium near infrared luminescent eutectic material [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]The preparation method of (2) is as follows:
(1) 77.4mg Yb (dbm) 3 (H 2 O) was dissolved in 10mL of toluene and stirred for 5min to give Yb (dbm) 3 (H 2 O) toluene solution;
(2) dissolving 22.5mg of S-configuration chiral single-double-tooth N-containing organic ligand L prepared by the method in 6mL of ethanol, and stirring for 5min to obtain an ethanol solution of L;
(3) 10mL Yb (dbm) 3 (H 2 O) (0.09 mmol) was added to 6mL of an ethanol solution containing N-containing organic ligand L (+) -2- (4 ',5' -pinene pyridyl-2 ') pyrazine (0.09 mmol) dissolved in chiral monodentate, stirred for 30min, filtered, the resulting clear solution was transferred into a test tube, and placed in an atmosphere of N-hexane to be naturally diffused, after 7 days, light yellow crystals were obtained, filtered, washed with 3mL of deionized water and 3mL of ethanol in sequence, and dried at room temperature to obtain a chiral ytterbium near infrared light emitting eutectic material with a yield of 91% (calculated as Yb).
The chiral ytterbium near-infrared luminescent eutectic material and the preparation method thereof provided by the invention are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (9)
1. A chiral ytterbium near infrared luminous eutectic material is characterized in that: the molecular formula of the chiral ytterbium near infrared luminescence eutectic material is [ Yb (dbm) 3 L]-[Yb(dbm) 3 C 2 H 5 OH]Wherein dbm is dibenzoylmethane anion and L is a chiral mono-bidentate N-containing organic ligand of S configuration: (+) -2- (4 ʹ,5 ʹ -pinene pyridinyl-2 ʹ) pyrazine;
the eutectic material is crystallized in a monoclinic system non-centrosymmetric space groupP2 1 The unit cell parameters are as follows:a = 10.3289(6) Å，b = 20.9947(12) Å，c = 21.4061(12) Å；α = γ = 90º，β = 98.852º(6)，V = 4586.7(5) Å 3 ，Z = 2，D c = 1.435 g∙cm –1 ，μ = 2.092 mm –1 ，R 1 = 0.0543，wR 2 = 0.0847。
2. the method for preparing the chiral ytterbium near infrared light emitting eutectic material of claim 1, which is characterized in that: the method comprises the following steps:
(1) yb (dbm) 3 (H 2 O) is dissolved in toluene and stirred for 5-10min to obtain Yb (dbm) 3 (H 2 O) toluene solution;
(2) dissolving chiral single-double-tooth N-containing organic ligand L in S configuration in ethanol, and stirring for 5-10min to obtain ethanol solution dissolved with L;
(3) the Yb (dbm) obtained in the step (1) is reacted with 3 (H 2 Adding the toluene solution of O) into the ethanol solution dissolved with L obtained in the step (2), continuously stirring at room temperature for 25-30min, filtering, transferring the obtained clear solution into a test tube, placing the test tube in the atmosphere of normal hexane for 5-7 days to obtain light yellow crystals, filtering, washing with deionized water and ethanol in sequence, and drying at room temperature to obtain the chiral ytterbium near infrared luminescent eutectic material.
3. The method for preparing the chiral ytterbium near infrared light emitting eutectic material according to claim 2, which is characterized in that: yb (dbm) of the step (1) 3 (H 2 Yb (dbm) in toluene solution of O) 3 (H 2 The concentration of O) is 0.008-0.02mol/L.
4. The method for preparing the chiral ytterbium near infrared light emitting eutectic material according to claim 2, which is characterized in that: the concentration of L in the ethanol solution containing the chiral single-double-tooth N organic ligand L in the step (2) is 0.01-0.035mol/L.
5. The method for preparing the chiral ytterbium near infrared light emitting eutectic material according to claim 2, which is characterized in that: yb (dbm) of the step (1) 3 (H 2 The ratio of O) to the amount of L material in step (2) is 1:1.
6. A hand according to claim 2The preparation method of the ytterbium near infrared luminescent eutectic material is characterized by comprising the following steps of: yb (dbm) in said step (3) 3 (H 2 The volume ratio of the toluene solution of O) to the ethanol solution of L is (5-12): 3-8.
7. The method for preparing the chiral ytterbium near infrared light emitting eutectic material according to claim 2, which is characterized in that: yb (dbm) of the step (1) 3 (H 2 The preparation method of O) is as follows: dissolving dibenzoylmethane in acetonitrile, stirring for 15-20min to obtain acetonitrile solution of dibenzoylmethane, adding ammonia water into acetonitrile solution, and dropwise adding Yb (CH) under continuous stirring 3 COO) 3 ·6H 2 O aqueous solution, precipitate, stirring for 2 hr to complete reaction, filtering, washing precipitate with small amount of deionized water, and vacuum drying to obtain light yellow Yb (dbm) 3 (H 2 O)。
8. The method for preparing the chiral ytterbium near infrared light emitting eutectic material according to claim 7, which is characterized in that: the mass volume ratio of the dibenzoylmethane to the acetonitrile is as follows: 1.0g, 6mL; the concentration of the ammonia water is 1mol/L; the Yb (CH) 3 COO) 3 ·6H 2 Yb (CH) in aqueous O solution 3 COO) 3 ·6H 2 The concentration of O was 0.262mol/L.
9. The method for preparing the chiral ytterbium near infrared light emitting eutectic material according to claim 8, which is characterized in that: the acetonitrile, ammonia water and Yb (CH) 3 COO) 3 ·6H 2 The volume ratio of the aqueous solution of O is 4:3:2.
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