WO2023201870A1 - 一种晶体及其制备方法和作为蓝色荧光闪烁材料的应用 - Google Patents

一种晶体及其制备方法和作为蓝色荧光闪烁材料的应用 Download PDF

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WO2023201870A1
WO2023201870A1 PCT/CN2022/099835 CN2022099835W WO2023201870A1 WO 2023201870 A1 WO2023201870 A1 WO 2023201870A1 CN 2022099835 W CN2022099835 W CN 2022099835W WO 2023201870 A1 WO2023201870 A1 WO 2023201870A1
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crystal
scintillation material
dmf
preparation
adba
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PCT/CN2022/099835
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French (fr)
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谢美娟
郑发鲲
王文飞
李宝义
高娟
郭国聪
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中国科学院福建物质结构研究所
闽都创新实验室
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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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • 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
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Definitions

  • the present application relates to a crystal, its preparation method and its application as a blue fluorescent scintillation material, and belongs to the technical field of luminescent crystal materials.
  • Scintillation materials are a type of functional material that can absorb X-rays, gamma rays or other high-energy particles and convert them into ultraviolet or visible light. They are widely used in radiation monitoring, safety inspections, industrial flaw detection, medical imaging and other fields.
  • Traditional scintillation materials are mainly divided into inorganic scintillation materials and organic scintillation materials.
  • Inorganic scintillation materials such as PbWO 4 , NaI:Tl, Bi 4 Ge 3 O 12 (BGO), etc., have excellent scintillation performance and high stability, but NaI :Tl is easy to deliquesce, which limits its application scope.
  • MOFs Metal-Organic Frameworks
  • MOFs are a type of porous coordination polymers with a periodic network structure composed of metal nodes and organic ligands connected. They have structure designability, performance tunability and low-cost solutions. Processing and other advantages, MOFs can take advantage of the synergistic effect of self-assembly of inorganic and organic primitives, and have great potential in the fields of radiation detection or medical imaging.
  • the object of the present invention is to provide a crystal and its preparation method and its application as a blue fluorescent scintillation material.
  • the crystal has good irradiation stability and exhibits blue fluorescence visible to the naked eye under ultraviolet light and X-ray irradiation. .
  • a crystal is provided, and the crystal has a one-dimensional structure
  • ADBA is a ligand formed by completely deprotonating hydrogen from 9,10-bis(4-carboxyphenyl)anthracene
  • DMF is N,N-dimethylformamide.
  • the crystal provided by the present invention is a one-dimensional chain composed of an infinite number of Pb 0.5 (ADBA) 0.5 (DMF) 0.5 structural units.
  • the chemical formula of the crystal is as shown in Formula II:
  • n in Formula II is ⁇ , which means continuous repetition and infinite extension.
  • the Pb in the crystal is a Pb 2+ metal ion in a five-coordination configuration; the Pb 2+ metal ions are respectively connected with four carboxylate groups from the two ADBA 2- ligands. O atom, O atom coordination on 1 DMF;
  • the crystal is a one-dimensional chain structure.
  • the crystal of the present invention belongs to the orthorhombic crystal system and has a Pnma space group structure.
  • the unit cell parameters of the crystal are:
  • the size of the crystal is 2mm ⁇ 2mm ⁇ 1.8mm.
  • a method for preparing the crystals described above is provided.
  • a mixed solution containing 9,10-bis(4-carboxyphenyl)anthracene, a lead source, an organic acid and a solvent is placed in a closed container for reaction. , to obtain the crystal.
  • the molar ratio of the lead source to the 9,10-bis(4-carboxyphenyl)anthracene is 1.8:1 to 2:1; the molar amount of the lead source is expressed in terms of the Pb element in the lead source. Molometer.
  • the molar ratio of the lead source to the 9,10-bis(4-carboxyphenyl)anthracene is 1.9:1 to 2:1; the molar amount of the lead source is expressed in terms of the Pb element in the lead source. Molometer.
  • the volume ratio of the amount of the lead source to the solvent is 0.1 mmol: 2 mL to 5 mL.
  • the volume ratio of the amount of the lead source to the solvent is 0.1 mmol:3 mL.
  • the lead source is selected from at least one of Pb(NO 3 ) 2 , PbCl 2 , and PbBr 2 .
  • the organic acid is o-fluorobenzoic acid.
  • the added amount of the organic acid is subject to adjusting the pH value of the mixed solution to 5-7.
  • the solvent is N,N-dimethylformamide.
  • reaction conditions are: temperature 80°C to 120°C, time 24h to 72h.
  • the reaction temperature is 90°C to 110°C, and the reaction time is 36h to 72h.
  • reaction temperature is independently selected from any value among 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C or a range between any two. value.
  • reaction time is independently selected from any value among 24h, 30h, 36h, 42h, 48h, 54h, 60h, 66h, 72h or any range value between the two.
  • the preparation method of the crystal includes:
  • a scintillation material is provided, and the scintillation material is selected from the above-mentioned crystals or crystals prepared by the above-mentioned method.
  • the crystal synthesized by the above method has good irradiation stability as a scintillation material.
  • the scintillation material emits blue fluorescence under ultraviolet light or X-ray irradiation.
  • the wavelength of the ultraviolet light is 320nm ⁇ 400nm.
  • the RGB color coordinates of the blue fluorescence are (0.16 ⁇ 0.20, 0.26 ⁇ 0.37).
  • the RGB color system color coordinates are (0.180 ⁇ 0.189, 0.274 ⁇ 0.354).
  • the RGB color system color coordinates are (0.184, 0.279).
  • the luminescence lifetime of the scintillation material is 4.5 ns to 6.0 ns.
  • the luminescence lifetime of the scintillation material is 5.20ns to 5.70ns.
  • the luminescence lifetime of the scintillation material is 5.53ns.
  • the crystal or the crystal prepared by the above-mentioned method or the above-mentioned scintillation material is provided in a blue fluorescent material, an X-ray radiation detection material, a radiation detection dosimeter, or a radiation imaging device. applications in.
  • the crystal provided by the present invention exhibits blue fluorescence visible to the naked eye under ultraviolet light with a wavelength of 365 nm and X-ray irradiation, and can be used to produce blue fluorescent materials, high-energy ray radiation detection materials and Devices, etc.
  • the preparation method of the crystal provided by the present invention is simple and suitable for large-scale industrial production.
  • the prepared crystal has high purity and good crystallinity as a blue fluorescent scintillation material, and has good X-ray response sensitivity. and irradiation stability.
  • Figure 1 is a schematic diagram of the coordination environment of sample 1#.
  • Figure 2 is the X-ray powder diffraction pattern of sample 1# crystal material [Pb(ADBA)(DMF)] n .
  • Figure 3 is the photoluminescence spectrum of sample 1# crystal material [Pb(ADBA)(DMF)] n .
  • Figure 4 is the luminescence color coordinate diagram of sample 1# crystal material [Pb(ADBA)(DMF)] n .
  • Figure 5 is the fluorescence luminescence lifetime spectrum of sample 1# crystal material [Pb(ADBA)(DMF)] n .
  • Figure 6 is the scintillation spectrum of sample 1# crystal material [Pb(ADBA)(DMF)] n .
  • Figure 7 is a linear chart of the n- flash fluorescence intensity of sample 1# crystal material [Pb(ADBA)(DMF)] as a function of X-ray dose.
  • Figure 8 is the irradiation stability diagram of sample 1# crystal material [Pb(ADBA)(DMF)] n .
  • the raw materials and reagents used in the present invention are purchased from commercial sources and used directly without treatment.
  • the instruments and equipment used adopt the protocols and parameters recommended by the manufacturers.
  • Test Example 1 Structural characterization of [Pb(ADBA)(DMF)] n crystal material
  • sample 1# prepared in Example 1 was characterized.
  • X-ray single crystal diffraction analysis results show that the structural formula of the crystalline material of sample 1# is [Pb(ADBA)(DMF)] n , which belongs to the Pnma space group of the orthorhombic crystal system.
  • the schematic diagram of the coordination environment of the crystal material [Pb(ADBA)(DMF)] n of sample 1# is shown in Figure 1.
  • the minimum asymmetric structural unit contains half of the Pb 2+ metal ion, half of the ADBA 2– ligand and Half of the coordinated DMF molecule.
  • the Pb 2+ metal ion is coordinated with five oxygen atoms, of which four O atoms come from the carboxylate groups of the two ADBA 2– ligands, and one O atom comes from the coordinated DMF molecule.
  • Its Pb–O bond length range is This results in a one-dimensional chain along the b-axis.
  • the photoluminescence performance test was performed on the sample 1# prepared in Example 1.
  • the fluorescence color coordinates were calculated and the RGB color coordinates of the blue light-emitting crystal material were (0.184, 0.279), indicating blue light emission (as shown in Figure 4).
  • the luminous life was tested using Edinburgh FL920 ns flash lamp and PMT detector.
  • the luminescence lifetime and fitting curve are shown in Figure 5.
  • the luminescence lifetime test shows that the lifetime of the sample 1# [Pb(ADBA)(DMF)] n crystal material is 5.53ns, and the lifetime is ns level, indicating that the blue light crystal is Fluorescent light.
  • Sample 1# prepared in Example 1 was subjected to a flicker luminescence performance test.
  • the scintillation luminescence test of sample 1#[Pb(ADBA)(DMF)] n crystal material was carried out on a self-built X-ray scintillation spectrometer.
  • the main part of the instrument is an Edinburgh FLS 920 fluorescence spectrometer, in which the excitation source is a high-purity tungsten target (model: MAGPRO X-ray sources).
  • the scintillation spectrum is shown in Figure 6. Under X-ray irradiation with constant tube voltage and different tube currents, the compound exhibits scintillation signals at 464nm, indicating that the compound has efficient X-ray response.
  • the scintillation luminescence intensity changes with the X-ray dose.
  • the linear chart is shown in Figure 7. As the X-ray dose increases, the scintillation signal intensity increases linearly, indicating a higher response sensitivity to X-rays.

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Abstract

本申请公开了一种晶体及其制备方法和作为蓝色荧光闪烁材料的应用，属于发光晶体材料技术领域。该晶体具有一维结构；最小不对称结构单元是Pb 0.5(ADBA) 0.5(DMF) 0.5；其中ADBA为9,10-二(4-羧基苯基)蒽完全脱质子氢后形成的配体；DMF为N,N-二甲基甲酰胺。该晶体作为蓝色荧光闪烁材料在紫外光和X射线照射下均表现出肉眼可见的蓝色荧光，在蓝色荧光材料、X射线辐射探测材料、辐射探测剂量计中具有潜在的应用价值。

Description

一种晶体及其制备方法和作为蓝色荧光闪烁材料的应用 技术领域
本申请涉及一种晶体及其制备方法和作为蓝色荧光闪烁材料的应用，属于发光晶体材料技术领域。
背景技术
闪烁材料是一类能够吸收X射线、γ射线或其它高能粒子，并将其转化为紫外或可见光的功能材料，广泛应用于辐射监测、安全检查、工业探伤、医学成像等领域。传统的闪烁材料主要分为无机闪烁材料和有机闪烁材料，其中无机闪烁材料如PbWO 4、NaI:Tl、Bi 4Ge 3O 12(BGO)等，具有优良的闪烁性能和高稳定性，但是NaI:Tl容易潮解，限制了其应用范围。PbWO 4、Bi 4Ge 3O 12(BGO)等大块晶体制备困难，生产成本高，机械强度差。有机闪烁体如萘、蒽、联四苯、1,3,5-三苯基苯及其衍生物等，虽然具有较快的衰减时间和发光强度，但是光产额较低，辐照稳定性差，并且在使用过程中极易氧化。金属有机框架(Metal-Organic Frameworks,MOFs)是一类由金属节点和有机配体连接组成的具有周期性网络结构的多孔配位聚合物，具有结构可设计性、性能可调性和低成本溶液加工过程等优势，MOFs可以利用无机基元和有机基元自组装的协同效应，在辐射探测或医学成像领域具有巨大的潜力。
发明内容
本发明的目的在于提供一种晶体及其制备方法和作为蓝色荧光闪烁材料的应用，该晶体具有良好的辐照稳定性，在紫外光和X射线照射下均表现出肉眼可见的蓝色荧光。
根据本发明的一个方面，提供了一种晶体，晶体为一维结构；
所述一维结构的最小不对称结构单元如式I所示；
Pb 0.5(ADBA) 0.5(DMF) 0.5      式I；
式I中，
ADBA为9,10-二(4-羧基苯基)蒽完全脱质子氢后形成的配体；
DMF为N,N-二甲基甲酰胺。
本发明提供的晶体是由无穷多个所述的Pb 0.5(ADBA) 0.5(DMF) 0.5结构单元构成的一维链状物，该晶体的化学式如式II所示：
[Pb(ADBA)(DMF)] n       式II；
式II中的n为∞，表示不断重复、无限延伸。
可选地，所述晶体中的Pb是五配位构型的Pb 2+金属离子；所述Pb 2+金属离子分别与来自于两个ADBA 2–配体的羧酸根基团上的四个O原子、1个DMF上的O原子配位；
所述晶体为一维链状结构。
可选地，本发明所述晶体属于正交晶系，具有Pnma空间群结构。
可选地，所述晶体的晶胞参数是：
Figure PCTCN2022099835-appb-000001
Figure PCTCN2022099835-appb-000002
可选地，
Figure PCTCN2022099835-appb-000003
Figure PCTCN2022099835-appb-000004
可选地，
Figure PCTCN2022099835-appb-000005
Figure PCTCN2022099835-appb-000006
可选地，晶胞参数中，α＝90°，β＝90°，γ＝90°，Z＝4，
Figure PCTCN2022099835-appb-000007
Figure PCTCN2022099835-appb-000008
可选地，所述晶体的尺寸为2mm×2mm×1.8mm。
根据本发明的另一方面，提供上述所述的晶体的制备方法，将含有9,10-二(4-羧基苯基)蒽、铅源、有机酸和溶剂的混合溶液置于密闭容器中反应，得到所述晶体。
可选地，所述铅源与所述9,10-二(4-羧基苯基)蒽的摩尔比为1.8:1～2:1；所述铅源的摩尔量以铅源中Pb元素的摩尔量计。
可选地，所述铅源与所述9,10-二(4-羧基苯基)蒽的摩尔比为 1.9:1～2:1；所述铅源的摩尔量以铅源中Pb元素的摩尔量计。
可选地，所述铅源的物质的量与所述溶剂的体积比为0.1mmol:2mL～5mL。
可选地，所述铅源的物质的量与所述溶剂的体积比为0.1mmol:3mL。
可选地，所述铅源选自Pb(NO 3) 2、PbCl 2、PbBr 2中的至少一种。
可选地，所述有机酸为邻氟苯甲酸。所述有机酸的加入量，以调节混合溶液的pH值至5～7为准。
可选地，所述溶剂为N,N-二甲基甲酰胺。
可选地，所述反应的条件为：温度为80℃～120℃，时间24h～72h。
可选地，反应温度为90℃～110℃，反应时间为36h～72h。
可选地，所述反应温度独立地选自80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃中的任意值或任意两者之间的范围值。
可选地，所述反应时间独立地选自24h、30h、36h、42h、48h、54h、60h、66h、72h中的任意值或任意两者之间的范围值。
作为一种优选的实施方式，所述的晶体的制备方法，包括：
将摩尔比为2:1的PbCl 2、9,10-二(4-羧基苯基)蒽放入容量为10mL的玻璃小瓶中，然后加入DMF溶剂，再加入邻氟苯甲酸调节pH值至5～7，进行溶剂热反应，PbCl 2与DMF的体积比为0.1mmol:3ml。反应温度为90℃，反应时间为72h，反应结束后冷却至室温，过滤用DMF洗涤后，得到黄色块状晶体，即为一维结构的[Pb(ADBA)(DMF)] n，其最小不对称结构单元Pb 0.5(ADBA) 0.5(DMF) 0.5。
根据本发明的再一方面，提供一种闪烁材料，所述闪烁材料选自上述所述晶体或上述的方法制备的得到的晶体。通过上述方法合成得到的晶体作为闪烁材料具有良好的辐照稳定性。
可选地，所述闪烁材料紫外光或X射线照射下发出蓝色荧光。
可选地，所述紫外光的波长为320nm～400nm。
可选地，所述蓝光荧光的RGB表色系色坐标为(0.16～0.20,0.26 ～0.37)。
可选地，所述RGB表色系色坐标为(0.180～0.189,0.274～0.354)。
可选地，所述RGB表色系色坐标为(0.184,0.279)。
优选地，所述闪烁材料的发光寿命为4.5ns～6.0ns。
优选地，所述闪烁材料的发光寿命为5.20ns～5.70ns。
更优选地，所述闪烁材料的发光寿命为5.53ns。
根据本发明的又一方面，提供所述晶体或上述所述的方法制备的得到的晶体或上述所述的闪烁材料在蓝色荧光材料、X射线辐射探测材料、辐射探测剂量计、辐射成像器件中的应用。
本发明能产生的有益效果包括：
(1)本发明所提供的晶体作为蓝色荧光闪烁材料，在波长365nm紫外光以及X射线照射下均表现出肉眼可见的蓝色荧光，可用于制作蓝色荧光材料、高能射线辐射探测材料及器件等。
(2)本发明所提供的晶体的制备方法，所述制备方法简单，适合大规模工业化生产，制备得到的晶体作为蓝色荧光闪烁材料纯度高，结晶度好，并且具有良好的X射线响应灵敏度和辐照稳定性。
附图说明
图1是样品1#的配位环境示意图。
图2是样品1#晶体材料[Pb(ADBA)(DMF)] n的X射线粉末衍射图。
图3是样品1#晶体材料[Pb(ADBA)(DMF)] n的光致发光谱图。
图4是样品1#晶体材料[Pb(ADBA)(DMF)] n的发光色坐标图。
图5是样品1#晶体材料[Pb(ADBA)(DMF)] n的荧光发光寿命谱图。
图6是样品1#晶体材料[Pb(ADBA)(DMF)] n的闪烁发光谱图。
图7是样品1#晶体材料[Pb(ADBA)(DMF)] n闪烁荧光强度随X射线剂量的线性图谱。
图8是样品1#晶体材料[Pb(ADBA)(DMF)] n的辐照稳定性图。
具体实施方式
下面结合实施例详述本发明，但本发明并不局限于这些实施例。
如无特别说明，本发明所用原料和试剂均来自商业购买，未经处理直接使用，所用仪器设备采用厂家推荐的方案和参数。
实施例1
按照2:1:6的摩尔量将PbCl 2(0.1mmol)、9,10-二(4-羧基苯基)蒽(0.05mmol)和邻氟苯甲酸(0.3mmol)放入容量为10mL的玻璃小瓶中，然后加入DMF(3ml)溶剂，得到pH＝6的混合溶液，所述混合溶液置于密闭容器中反应，反应温度为90℃，反应时间为48h，反应结束后冷却至室温，过滤用DMF洗涤后得到黄色块状晶体[Pb(ADBA)(DMF)] n，记为样品1#。
实施例2
按照2:1:6的摩尔量将Pb(NO 3) 2(0.1mmol)、9,10-二(4-羧基苯基)蒽(0.05mmol)和邻氟苯甲酸(0.3mmol)放入容量为10mL的玻璃小瓶中，然后加入DMF(3ml)溶剂，得到pH＝6的混合溶液，所述混合溶液置于密闭容器中反应，反应温度为90℃，反应时间为72h，反应结束后冷却至室温，过滤用DMF洗涤后得到黄色块状晶体[Pb(ADBA)(DMF)] n，记为样品2#。
实施例3
按照2:1:6的摩尔量将PbCl 2(0.1mmol)、9,10-二(4-羧基苯基)蒽(0.05mmol)和邻氟苯甲酸(0.3mmol)放入容量为10mL的玻璃小瓶中，然后加入DMF(3ml)溶剂，得到pH＝6的混合溶液，所述混合溶液置于密闭容器中反应，反应温度为100℃，反应时间为48h，反应结束后冷却至室温，过滤用DMF洗涤后得到黄色块状晶体[Pb(ADBA)(DMF)] n，记为样品3#。
实施例4
按照2:1:6的摩尔量将PbBr 2(0.1mmol)、9,10-二(4-羧基苯基)蒽(0.05mmol)和邻氟苯甲酸(0.3mmol)放入容量为10mL的玻璃小瓶中，然后加入DMF(3ml)溶剂，得到pH＝6的混合溶液，所述混合溶液置于密闭容器中反应，反应温度为100℃，反应时间为72h，反应结束后冷却至室温，过滤用DMF洗涤后得到黄色块状晶体[Pb(ADBA)(DMF)] n，记为样品4#。
测试例1[Pb(ADBA)(DMF)] n晶体材料的结构表征
对实施例1制备得到的样品1#进行结构表征。
将样品1#[Pb(ADBA)(DMF)] n在Rigaku FR-X型单晶衍射仪上进行X射线单晶衍射测试(测试条件：Mo靶，K α辐射源(λ＝0.07107nm)，测试温度293K)后，通过Olex 2 1.2对结构进行解析。
X射线单晶衍射解析结果表明：样品1#的晶态材料结构式为[Pb(ADBA)(DMF)] n，属于正交晶系的Pnma空间群。晶胞参数为
Figure PCTCN2022099835-appb-000009
Figure PCTCN2022099835-appb-000010
α＝90°，β＝90°，γ＝90°，Z＝4，
Figure PCTCN2022099835-appb-000011
样品1#的晶体材料[Pb(ADBA)(DMF)] n的配位环境示意图如附图1所示，最小不对称结构单元包含半个Pb 2+金属离子，半个ADBA 2–配体以及半个配位的DMF分子。Pb 2+金属离子和五个氧原子配位，其中四个O原子来自于两个ADBA 2–配体的羧酸根基团，一个O原子来自于配位的DMF分子。其Pb–O键长范围为
Figure PCTCN2022099835-appb-000012
从而形成沿着b轴的一维链。
样品1#的X射线粉末衍射谱图如附图2所示，实验结果(1代表样品1#)与模拟结果(模拟线)保持一致，表明材料为纯相。
采用与上述相同的方法测试样品2#、3#和4#。样品2#、3#和4#的X射线单晶衍射解析结果与样品1#的一致；样品2#、3#和4#的XRD测试结果和样品1#的一致。
测试例2[Pb(ADBA)(DMF)] n晶体材料的光致发光性能测试
对实施例1制备得到的样品1#进行光致发光性能测试。
样品1#[Pb(ADBA)(DMF)] n晶体材料的光致发光性能测试在Edinburgh FL920上进行。
激发和发射光谱如附图3所示，在410nm最佳波长的激发下，化合物在470nm表现出蓝光发射。
荧光色坐标计算得该蓝光发光晶体材料的RGB表色系色坐标为(0.184,0.279)，为蓝光发光(如图4所示)。
用Edinburgh FL920的ns闪光灯和PMT探测器对其发光寿命进行测试。发光寿命及拟合曲线如附图5所示，发光寿命测试表明，样品1#[Pb(ADBA)(DMF)] n晶体材料的寿命是5.53ns，寿命为ns级，表明所述蓝光晶体为荧光发光。
采用与上述相同的方法测试样品2#、3#和4#。样品2#、3#和4#的光致发光性能测试结果和样品1#保持一致。
测试例3[Pb(ADBA)(DMF)] n晶体材料的闪烁发光性能测试
对实施例1制备得到的样品1#进行闪烁发光性能测试。
样品1#[Pb(ADBA)(DMF)] n晶体材料的闪烁发光测试在自主搭建的X射线闪烁谱仪上进行。仪器的主体部分为Edinburgh FLS 920荧光光谱仪，其中激发源为高纯钨靶(型号：
Figure PCTCN2022099835-appb-000013
MAGPRO X-ray sources)。闪烁发光谱图如附图6，在恒定管电压，不同管电流的X射线照射下，化合物在均在464nm处表现出闪烁信号，表明了化合物具有高效的X射线响应闪烁发光强度随X射线剂量的线性图谱如附图7，随着X射线剂量的增加，闪烁信号强度线性增加，对X射线具有较高的响应灵敏度。
采用与上述相同的方法测试样品2#、3#和4#。样品2#、3#和4#的闪烁发光性能测试结果和样品1#保持一致。
测试例4[Pb(ADBA)(DMF)] n晶体材料的辐照稳定性测试
对实施例1制备得到的样品1#进行辐照稳定性测试。
样品1#[Pb(ADBA)(DMF)] n晶体材料的辐照稳定性测试在自主搭建的X射线闪烁谱仪上进行。将样品在连续高剂量率X射线下进行辐照，并记录其发光强度，如图8所示，发现辐照累积剂量456Gy时没有明显的光猝灭，可见其具有良好的辐照稳定性。
采用与上述相同的方法测试样品2#、3#和4#。样品2#、3#和4#的辐照稳定性测试结果和样品1#保持一致。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (27)

  1. 一种晶体，其特征在于，所述晶体具有一维结构；
    所述一维结构的最小不对称结构单元如式I所示；
    Pb 0.5(ADBA) 0.5(DMF) 0.5  式I；
    式I中，
    ADBA为9,10-二(4-羧基苯基)蒽完全脱质子氢后形成的配体；
    DMF为N,N-二甲基甲酰胺。
  2. 根据权利要求1所述的晶体，其特征在于，所述晶体中的Pb是五配位构型的Pb 2+金属离子；
    所述Pb 2+金属离子分别与来自于两个ADBA 2–配体的羧酸根基团上的四个O原子、1个DMF上的O原子配位；
    所述晶体为一维链状结构。
  3. 根据权利要求1所述的晶体，其特征在于，所述晶体属于正交晶系，具有Pnma空间群结构。
  4. 根据权利要求1所述的晶体，其特征在于，所述晶体的晶胞参数是：
    Figure PCTCN2022099835-appb-100001
    Figure PCTCN2022099835-appb-100002
  5. 根据权利要求1所述的晶体，其特征在于，所述晶体的晶胞参数是：
    Figure PCTCN2022099835-appb-100003
    Figure PCTCN2022099835-appb-100004
  6. 根据权利要求1所述的晶体，其特征在于，
    Figure PCTCN2022099835-appb-100005
    Figure PCTCN2022099835-appb-100006
  7. 根据权利要求1所述的晶体，其特征在于，晶胞参数中，α＝90°，β＝90°，γ＝90°，Z＝4，
    Figure PCTCN2022099835-appb-100007
  8. 根据权利要求1所述的晶体，其特征在于，所述晶体的尺寸为2mm×2mm×1.8mm。
  9. 权利要求1-8任一项所述的晶体的制备方法，其特征在于，将含有9,10-二(4-羧基苯基)蒽、铅源、有机酸和溶剂的混合溶液置于密闭容器中反应，得到所述晶体。
  10. 根据权利要求9所述的制备方法，其特征在于，所述铅源与所述9,10-二(4-羧基苯基)蒽的摩尔比为1.8:1～2:1；
    所述铅源的摩尔量以铅源中Pb元素的摩尔量计。
  11. 根据权利要求9所述的制备方法，其特征在于，所述铅源的物质的量与所述溶剂的体积比为0.1mmol:2mL～5mL。
  12. 根据权利要求9所述的制备方法，其特征在于，所述铅源选自Pb(NO 3) 2、PbCl 2、PbBr 2中的至少一种。
  13. 根据权利要求9所述的制备方法，其特征在于，所述有机酸为邻氟苯甲酸。
  14. 根据权利要求9所述的制备方法，其特征在于，所述有机酸将混合溶液的pH值调节至为5～7。
  15. 根据权利要求9所述的制备方法，其特征在于，所述溶剂为N,N-二甲基甲酰胺。
  16. 根据权利要求9所述的制备方法，其特征在于，所述反应 的温度为80℃～120℃，反应的时间24h～72h。
  17. 根据权利要求9所述的制备方法，其特征在于，反应的温度为90℃～100℃，反应的时间为36h～72h。
  18. 一种闪烁材料，其特征在于，所述闪烁材料选自权利要求1-8任一项所述的晶体和/或权利要求9-17任一项所述的方法制备的得到的晶体。
  19. 根据权利要求18所述的闪烁材料，其特征在于，所述闪烁材料紫外光或X射线照射下发出蓝色荧光。
  20. 根据权利要求18所述的闪烁材料，其特征在于，所述紫外光的波长为320nm～400nm。
  21. 根据权利要求18所述的闪烁材料，其特征在于，所述蓝光荧光的RGB表色系色坐标为(0.16～0.20,0.26～0.37)。
  22. 根据权利要求18所述的闪烁材料，其特征在于，所述RGB表色系色坐标为(0.180～0.189,0.274～0.354)；
  23. 根据权利要求18所述的闪烁材料，其特征在于，所述RGB表色系色坐标为(0.184,0.279)。
  24. 根据权利要求18所述的闪烁材料，其特征在于，所述闪烁材料的发光寿命为4.5ns～6.0ns。
  25. 根据权利要求18所述的闪烁材料，其特征在于，所述闪烁材料的发光寿命为5.20ns～5.70ns。
  26. 根据权利要求18所述的闪烁材料，其特征在于，所述闪烁材料的发光寿命为5.53ns。
  27. 权利要求1-8任一项所述的晶体、权利要求9-17任一项所述的方法制备的得到的晶体、或权利要求18-26任一项所述的闪烁材料在蓝色荧光材料、X射线辐射探测材料、辐射探测剂量计、辐射成像器件中的应用。
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