CN107417928A - 一种含混合配体的金属银配位聚合物及其制备方法 - Google Patents

一种含混合配体的金属银配位聚合物及其制备方法 Download PDF

Info

Publication number
CN107417928A
CN107417928A CN201710835672.8A CN201710835672A CN107417928A CN 107417928 A CN107417928 A CN 107417928A CN 201710835672 A CN201710835672 A CN 201710835672A CN 107417928 A CN107417928 A CN 107417928A
Authority
CN
China
Prior art keywords
coordination polymer
metallic silver
containing mixed
mixed ligand
polymer containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710835672.8A
Other languages
English (en)
Other versions
CN107417928B (zh
Inventor
汪永涛
张晓龙
汤桂梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN201710835672.8A priority Critical patent/CN107417928B/zh
Publication of CN107417928A publication Critical patent/CN107417928A/zh
Application granted granted Critical
Publication of CN107417928B publication Critical patent/CN107417928B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

本发明涉及配位聚合物方面的合成，具体公开了一种含混合配体的金属银配位聚合物及其制备方法。一种含混合配体的金属银配位聚合物，化学式为：[Ag(BS)(BPP)2]n。其中BS为苯磺酸根，DPP为1,3‑二(4‑吡啶基)丙烷。具体方法如下：将BS配体和DPP配体和金属盐以一定比例的物质的量混合溶于水和甲醇的混合溶液中，加入一定量的氢氧化钠，室温晶化3天，析出块状晶体。此配位聚合物的制备方法工艺简单，无污染，结晶度高。该含有混合配体的金属银配位聚合物在发光领域具有非常好的潜在应用前景。

Description

一种含混合配体的金属银配位聚合物及其制备方法
技术领域
本发明属于金属有机配位聚合物、荧光材料领域，涉及到一种含混合配体的金属银配位聚合物的制备和应用。
技术背景
配位聚合物是指有机配体通过配位键、氢键和共价键等作用方式，与金属离子自组装形成的具有高度规整无线网络结构的配合物。金属配位聚合物作为一种新型的功能材料在气体催化、气体吸收或存储、传感、药物运输和荧光等方面有着潜在的应用价值。
近年来，由金属银离子与有机磺酸分子建筑块自组装形成的芳香磺酸银配合物备受国内外化学家们的关注。主要是因为：(1)银离子具有较宽范围的配位数和丰富的配位多面体构型，并且根据软硬酸碱理论，银离子与磺酸阴离子间有着良好的配位倾向，能够通过配位键构筑出具有稳定结构的磺酸银配合物；(2)磺酸基团的3 个氧原子可以从不同的方向桥联金属银离子形成不同维数甚至具有微孔结构的配合物；(3)目前报道的很多磺酸银配合物具有较好的荧光、选择性吸附以及离子交换等特性。而且第二配体的存在对磺酸银化合物的结构会产生很大的影响。因此本发明考虑到上述优点，采用苯磺酸和银离子及中性配体配位形成金属配位聚合物(Lei Z X, Zhu Q Y, Zhang X, et al. Inorg. Chem.,2010,49(10):4385-4387）。
发明内容
本发明提供了一种含混合配体的金属银配位聚合物及其制备方法。
本发明提供的一种含混合配体的金属银配位聚合物，化学式为: [Ag(BS)(BPP)2]n。
本发明提供的一种含混合配体的金属银配位聚合物主要采取以下技术方案：
将苯磺酸、氢氧化钠、硝酸银以及DPP (1,3-二(吡啶-4-基)丙烷) 溶于水和甲醇的混合溶液中。然后将混合溶液在常温下反应一定时间后，过滤析出白色块状配位聚合物。
本发明的优点：本发明提供的一种含混合配体的金属银配位聚合物的制备工艺简单，原料便宜，产率较高，样品纯度高，并且在荧光领域具有良好的潜在应用前景。
附图说明
图1、本发明所述的一种含混合配体的金属银配位聚合物的Ag离子的配位环境图。
图2、本发明所述的一种含混合配体的金属银配位聚合物的一维链状图。
图3、本发明所述的一种含混合配体的金属银配位聚合物的二维结构图。
图4、本发明所述的一种含混合配体的金属银配位聚合物的堆积图。
图5、本发明所述的一种含混合配体的金属银配位聚合物的固态荧光光谱图。
具体实施方式
下面结合实例对本发明进行详细的说明，实施例仅是本发明的优先实施方式，不是对本发明的限制。
实施例1（C19H19AgN2O3S）
苯磺酸、氢氧化钠、DPP (1,3-二(吡啶-4-基)丙烷)和硝酸银的比例为0.1~3.5:0.1~3.5:0.1~3.5:0.1~3.5；有机溶剂甲醇与水的比例为1:1~3；反应时间为0.5~72小时。过滤析出白色块状晶体。
将上述含混合配体的金属银配位聚合物进行表征
晶体X-射线衍射数据采用Burkcer Smart CCD单晶衍射仪测定。MoKa辐射(λ=0 .71073Å )，石墨单色器，以ω扫描方式收集数据，并进行Lp因子校正和经验吸收校正。先用直接法确定金属原子及部分其他非氢原子的位置，然后用差值函数法和最小二乘法求出其余全部非氢原子坐标，并用理论加氢法得到氢原子位置或从差值傅立叶图上找到，用全矩阵最小二乘法对结构进行修正。晶体结构图见图1-4。
图1为本发明所述的含混合配体的金属银配位聚合物的Ag离子的配位环境图。如图1所示，从晶体结构分析可以看到，该配位聚合物属于单斜晶系，P21/n空间群，其中每个不对称单元含有一个Ag(I)离子，一个DPP，一个BS阴离子，中心银离子是四配位，分别与BS上的两个O原子和两个DPP上的N原子配位。Ag-O的键长距离范围是2.8081(18)到2.8237(19) Å，Ag-N的键长范围距离是2.1487(17)Å到2.1502(17)Å。
图2为本发明所述的含混合配体的金属银配位聚合物的一维链状图。如图2所示，以金属中心Ag的配位的一维链状图。如图所示，每一个相连的Ag(I)通过DPP配体桥联形成一维链状结构。
图3为本发明所述的含混合配体的金属银配位聚合物的二维结构图。如图3所示，DPP中的碳原子与BS阴离子中的氧原子形成分子内氢键（C-H∙∙∙O），其键长和键角分别是2.54 Å和177°。通过氢键使得从一维链延伸到二维层状结构。
图4为本发明所述的含混合配体的金属银配位聚合物的堆积图。除了通过氢键的作用外，还存在芳香环之间的π∙∙∙π堆积。这些超分子作用力使二维层状延伸至三维超分子结构。
图5是本发明所述的含混合配体的金属银配位聚合物的固态荧光光谱图。如图5所示，配体BS的激发波长为420nm时，在518nm出现最大发射峰;含氮配体DPP的激发波长为362nm时，在410nm出现最大发射峰。化合物的激发波长为332nm时，在388nm处出现最大发射峰，与配体BS和DPP相比分别发生了130nm和22nm的蓝移。化合物的发光是源自磺酸根离子和/或中性配体的能记得跃迁。发射带的移动归因于磺酸脱质子和磺酸根离子与中性配体对银离子的配位。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应落在本发明的保护范围之内。

Claims (4)

1.含混合配体的金属银配位聚合物，其特征在于所述聚合物的分子式为C19H19AgN2O3S。
2.含混合配体的金属银配位聚合物，其特征在于所述的金属银配位聚合物为单斜晶系，P21/n空间群，晶胞参数为a= 10.3444(3)Å, b= 9.5715(3)Å, c= 18.7223(5)Å, α=90°, β=96.374(2)°, γ=90°,V= 1842.26(9)Å3; 该银离子呈现四配位结构，Ag离子分别与两个不同1,3-二(吡啶-4-基)丙烷上的N原子，苯磺酸根上的两个O原子配位。
3.根据权利要求1所述的含混合配体的金属银配位聚合物，其特征在于所使用的苯磺酸、氢氧化钠、DPP (1,3-二(吡啶-4-基)丙烷)和硝酸银的比例为0.1~3.5:0.1~3.5:0.1~3.5:0.1~3.5；有机溶剂甲醇与水的比例为1:1~3；反应时间为0.5~72小时。
4.根据权利要求书1所述的含混合配体金属银配位聚合物，其特征在于含混合配体金属银配位聚合物可作为荧光发光材料。
CN201710835672.8A 2017-09-16 2017-09-16 一种含混合配体的金属银配位聚合物及其制备方法 Expired - Fee Related CN107417928B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710835672.8A CN107417928B (zh) 2017-09-16 2017-09-16 一种含混合配体的金属银配位聚合物及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710835672.8A CN107417928B (zh) 2017-09-16 2017-09-16 一种含混合配体的金属银配位聚合物及其制备方法

Publications (2)

Publication Number Publication Date
CN107417928A true CN107417928A (zh) 2017-12-01
CN107417928B CN107417928B (zh) 2021-04-13

Family

ID=60433035

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710835672.8A Expired - Fee Related CN107417928B (zh) 2017-09-16 2017-09-16 一种含混合配体的金属银配位聚合物及其制备方法

Country Status (1)

Country Link
CN (1) CN107417928B (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108102110A (zh) * 2018-01-15 2018-06-01 齐鲁工业大学 一种苯磺酸银配位聚合物及其制备方法
CN108239288A (zh) * 2018-01-15 2018-07-03 齐鲁工业大学 一种基于磺酸类金属银配位聚合物及其制备方法
CN108373539A (zh) * 2018-01-15 2018-08-07 齐鲁工业大学 一种具有中性配体的磺酸金属配位聚合物及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011089571A2 (en) * 2010-01-21 2011-07-28 L'oreal A cosmetic composition including at least one fluorophore compound
CN102227437A (zh) * 2008-12-01 2011-10-26 住友化学株式会社 发光性银络合物
CN103936791A (zh) * 2013-12-12 2014-07-23 石家庄诚志永华显示材料有限公司 一系列有机电致磷光材料
CN105001164A (zh) * 2015-07-02 2015-10-28 齐鲁工业大学 含对甲苯磺酸的金属配位聚合物的合成及其催化活性
CN105017333A (zh) * 2015-07-01 2015-11-04 齐鲁工业大学 一种催化剂催化二氢嘧啶酮类化合物的合成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102227437A (zh) * 2008-12-01 2011-10-26 住友化学株式会社 发光性银络合物
WO2011089571A2 (en) * 2010-01-21 2011-07-28 L'oreal A cosmetic composition including at least one fluorophore compound
CN103936791A (zh) * 2013-12-12 2014-07-23 石家庄诚志永华显示材料有限公司 一系列有机电致磷光材料
CN105017333A (zh) * 2015-07-01 2015-11-04 齐鲁工业大学 一种催化剂催化二氢嘧啶酮类化合物的合成方法
CN105001164A (zh) * 2015-07-02 2015-10-28 齐鲁工业大学 含对甲苯磺酸的金属配位聚合物的合成及其催化活性

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
FANG-FANG LI等: "Syntheses, Structures, and Characterizations of Four New Silver(I) Sulfonate Coordination Polymers with Neutral Ligands", 《CRYSTAL GROWTH & DESIGN》 *
GEORGE K.H. SHIMIZU等: "A layered silver sulfonate incorporating nine-coordinate AgI in a hexagonal grid", 《CHEMICAL COMMUNICATIONS》 *
刘海燕等: "磺酸银配位聚合物的研究进展", 《化学世界》 *
董宪武: "含中性配体的磺酸银配位聚合物的合成、结构及性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
郝洪庆等: "基于4-二苯基乙酸及1,3-二(4-吡啶基)丙烷的两个银配合物的结构和荧光", 《无机化学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108102110A (zh) * 2018-01-15 2018-06-01 齐鲁工业大学 一种苯磺酸银配位聚合物及其制备方法
CN108239288A (zh) * 2018-01-15 2018-07-03 齐鲁工业大学 一种基于磺酸类金属银配位聚合物及其制备方法
CN108373539A (zh) * 2018-01-15 2018-08-07 齐鲁工业大学 一种具有中性配体的磺酸金属配位聚合物及其制备方法

Also Published As

Publication number Publication date
CN107417928B (zh) 2021-04-13

Similar Documents

Publication Publication Date Title
Wang et al. Effect of flexible bis-pyridyl-bis-amide ligands and dicarboxylates on the assembly and properties of multifunctional Cu (II) metal–organic coordination polymers
Hu et al. d 10 Metal complexes assembled from isomeric benzenedicarboxylates and 3-(2-pyridyl) pyrazole showing 1D chain structures: syntheses, structures and luminescent properties
Wang et al. Polycarboxylate-directed various Co (ii) complexes based on a “V”-like bis-pyridyl-bis-amide derivative: construction, electrochemical and photocatalytic properties
Ye et al. N-donor ligands enhancing luminescence properties of seven Zn/Cd (II) MOFs based on a large rigid π-conjugated carboxylate ligand
Liu et al. pH-dependent solvothermal formation of two different 3D multiple interpenetrating nets from the same components of Zn (NO 3) 2, 1, 3-benzenedicarboxylate and 1, 4-bis [2-(4-pyridyl) ethenyl] benzene
Xu et al. Syntheses, crystal structures and luminescent properties of four Zn (ii) coordination polymers with pyrazolone derivatives and 4, 4′-bipyridine
Wang et al. Two polyoxometalate-directed 3D metal–organic frameworks with multinuclear silver–ptz cycle/belts as subunits
Cheng et al. Substituted groups-directed assembly of Cd (II) coordination polymers based on 5-R-1, 3-benzenedicarboxylate and 4, 4'-bis (1-imidazolyl) bibenzene: syntheses, structures and photoluminescent properties
Yang et al. Synthesis, crystal structures, and luminescence properties of seven tripodal imidazole-based Zn/Cd (II) coordination polymers induced by tricarboxylates
Fang et al. Construction of three high-dimensional supramolecular networks from temperature-driven conformational isomers
CN107417928A (zh) 一种含混合配体的金属银配位聚合物及其制备方法
Mironov et al. New mixed-ligand cyanohydroxo octahedral cluster complex trans-[Re 6 S 8 (CN) 2 (OH) 4] 4−, its luminescence properties and chemical reactivity
Liu et al. Series of Organic–Inorganic Hybrid Rare Earth Derivatives Based on [MnV13O38] 7–Polyoxoanion: Syntheses, Structures, and Magnetic and Electrochemical Properties
Wang et al. Rational Synthesis and Characterization of Two Three‐Dimensional Metal‐Organic Frameworks Incorporating Silver Chains and 1, 2, 3, 4, 5, 6‐Cyclohexanehexacarboxylate
Wang et al. Polyoxometalate-directed assembly and various structures of inorganic–organic hybrid compounds based on a semi-rigid bis-pyridyl-bis-amide
Buvailo et al. Copper-containing hybrid compounds based on extremely rare [V 2 Mo 6 O 26] 6–POM as water oxidation catalysts
Sapianik et al. Metal-organic frameworks from pre-synthesized heterometallic (df) complexes: Synthesis, structure and luminescent properties
Xu et al. Solvent-induced Mn (II)/Zn (II)/Co (II) organopolymolybdate compounds constructed by bis-pyridyl-bis-amide ligands through the Mo–N bond: synthesis, structures and properties
Politeo et al. The first coordination compound of 6-fluoronicotinate: the crystal structure of a one-dimensional nickel (II) coordination polymer containing the mixed ligands 6-fluoronicotinate and 4, 4′-bipyridine
Wang et al. A series of new polyoxometalate-based metal–organic complexes with different rigid pyridyl-bis (triazole) ligands: assembly, structures and electrochemical properties
Yan et al. Two cationic [(Cu x I y) x− y] n motif based coordination polymers and their photocatalytic properties
Wang et al. Metal–organic coordination architectures of bis (N-imidazolyl) pyridazine: Syntheses, structures, emission and photocatalytic properties
Wu et al. Two 2D sliver complexes with a symmetric and noncentrosymmetric architecture controlled by the metal–ligand ratio
Song et al. Lanthanide‐Coordination Polymers with Pyridinedicarboxylic Acids: Syntheses, Structures, and Luminescent Properties
Chen et al. Adjusting the structures of lanthanide (III) complexes by variation of the metal sources: From a 2D (32.4)(34.43. 52.65. 7) layer to an unusual 3D (412.63)(49.66) nia network

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210413

Termination date: 20210916

CF01 Termination of patent right due to non-payment of annual fee