CN112961172A - 一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物及制备方法 - Google Patents
一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物及制备方法 Download PDFInfo
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011701 zinc Substances 0.000 title claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 20
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 125000001246 bromo group Chemical group Br* 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VUTICWRXMKBOSF-UHFFFAOYSA-N 2,5-dibromoterephthalic acid Chemical compound OC(=O)C1=CC(Br)=C(C(O)=O)C=C1Br VUTICWRXMKBOSF-UHFFFAOYSA-N 0.000 claims abstract description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002447 crystallographic data Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229960001763 zinc sulfate Drugs 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 description 9
- 239000013256 coordination polymer Substances 0.000 description 5
- 229920001795 coordination polymer Polymers 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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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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- Pyridine Compounds (AREA)
Abstract
Description
技术领域
本发明属于金属有机配合物制备技术领域,特别涉及一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物[ZnL(2,2′-bipy)(H2O)]n(H2L为2,5-二溴对苯二甲酸,2,2′-bipy为2,2′-联吡啶)的结构及其制备方法。
背景技术
近年来,基于金属和有机配体间的超分子作用来设计和构筑超分子化学体系已然成为材料科学、配位化学等领域内充满前景的研究课题之一。金属-有机框架化合物(MOFs)因结构的特殊性而具有重要的研究意义,备受广大科研工作者的广泛关注。对苯二甲酸属于芳香族多元羧酸化合物,是常用的一种配体,能够与金属离子构筑出多种形式不同、强刚性和优良稳定性的配位聚合物。目前利用对苯二甲酸作为多羧酸基配体构筑配位聚合物的研究甚少,一些报道的配位聚合物制备过程复杂,不易重现。2,5-二溴对苯二甲酸具有含溴侧链,可以通过分子间卤键相互作用构筑配合物结构时,为制备新型的多维配位聚合物提供了一种选择。
本申请提供了一种以2,5-二溴对苯二甲酸、2,2′-联吡啶和硫酸锌为原料,通过水热法,获得了化学式为[ZnL(2,2′-bipy)(H2O)]n锌配合物的结构及其制备方法。
发明内容
本发明的目的:提供一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物及制备方法。
本发明的思路:基于卤键是由卤原子(路易斯酸)与中性的或者带负电的路易斯碱之间形成的非共价相互作用,是一种类似氢键的分子间弱相互作用,能广泛应用于构筑配位聚合物的研究思路,选择含溴侧链配体----2,5-二溴对苯二甲酸 (H2L)为主配体、2,2′-联吡啶(2,2′-bipy)为辅助配体和过渡金属锌盐(硫酸锌)为原料,通过水热法获得2,5-二溴对苯二甲酸锌配合物。
含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物结构特点:其化学式[ZnL(2,2′-bipy)(H2O)]n(H2L=2,5-二溴对苯二甲酸;2,2′-bipy=2,2′-联吡啶),属于单斜晶系,空间群为P21/c,晶胞参数为 α=90°,β=97.0940(10)°,γ=90°,Z=4,表1 为该锌配合物的晶体数据,表2为该锌配合物部分键长和键角。
表1.[ZnL(2,2′-bipy)(H2O)]n的晶体学数据
以上所述含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物的制备方法:
(1)称量0.0575g ZnSO4·7H2O、0.0648g 2,5-二溴对苯二甲酸和0.0312g 2,2′-联吡啶溶于溶于含有6mL N,N-二甲基甲酰胺(DMF)和4mL蒸馏水的烧杯中,室温下,将混合溶液用磁力搅拌器搅拌30min,制得混合溶液;
(2)将步骤(2)制得的混合溶液转入25mL带有聚四氟乙烯瓶的反应釜中,放入烘箱加热至90℃,反应72h后,以10℃·h-1的速率降温至60℃,再保温2h,关闭烘箱让其在自然状态下冷却至室温后,取出反应釜,有无色透明块状晶体生成,即得到一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物。
本发明的制备方法具有工艺简单、易操作,具有良好的重现性,污染少等优点,制备的[ZnL(2,2′-bipy)(H2O)]n纯度高,为制备芳香族多元羧酸过渡金属配合物提供了一条新的途径。
附图说明
图1是本发明化学式为[ZnL(2,2′-bipy)(H2O)]n锌配合物的分子结构椭球图。
图2是本发明化学式为[ZnL(2,2′-bipy)(H2O)]n锌配合物的多面体图。
图3是本发明化学式为[ZnL(2,2′-bipy)(H2O)]n锌配合物的三维堆积图(沿a 方向)。
具体实施方式
实施例1:
(1)称量0.0575g ZnSO4·7H2O、0.0648g 2,5-二溴对苯二甲酸和0.0312g 2,2′-联吡啶(2,2′-bipy)溶于溶于含有6mL N,N-二甲基甲酰胺和4mL蒸馏水的烧杯中;
(2)室温下,将步骤(1)烧杯中的溶液用磁力搅拌器搅拌30min,制得混合溶液;
(3)将步骤(2)制得的混合溶液转入25mL带有聚四氟乙烯瓶的反应釜中,放入烘箱加热至90℃,反应72h后,以10℃·h-1的速率降温至60℃,再保温2h,关闭烘箱让其在自然状态下冷却至室温后,取出反应釜,有无色透明块状晶体生成,即得到一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物。产率为57.2%。通过单晶衍射仪测定[ZnL(2,2′-bipy)(H2O)]n的结构,晶体学数据见表1,键长键角数据见表2。
(4)含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物结构分析:
元素分析理论值按C18H12Br2N2O5Zn计算(%):C,38.47;N,4.97;H,2.14。实测值(%):C,38.56;N,4.85;H,2.19。
从附图图1可以看出,该配合物的基本单元由1个Zn(Ⅱ)中心离子、2个主配体2,5-二溴对苯二甲酸阴离子、1个辅助配体2,2′-联吡啶和1个配位水分子组成。每个Zn(Ⅱ)离子与配体2,5-二溴对苯二甲酸的2个羧基氧原子,2,2′-联吡啶的2个氮原子以及1个配位水分子的氧原子配位,形成五配位结构(对称码:(a) -x,-y,-z+1;(b)-x+1,-y,-z+1)。结合表2和附图图2可以看出:每个配位原子 O2、O3、N2与中心原子Zn(II)离子形成的键角之和为359.71°,接近理想的360°,说明这3个配位原子组成了赤道平面,且有较好的平面性。配体上的O4、N1位于轴向位置,轴向键角O4-Zn1-N1(159.11°)显示出配合物为三角双锥构型。配位键Zn-O键长为1.900(2)~2.0628(19)之间,Zn-N键长处于2.073(2)~2.115(2) 键角O-Zn-X(X=O,N)处于89.03(8)~169.11(9)°,都在正常的范围内。
由附图图3可知,该配合物以Zn2+为节点,L2-和2,2′-bipy为连接体相互连接,形成无限延续长的一维链状结构,链与链之间通过O-H···O分子氢键作用,有序堆积形成二维结构。
Claims (1)
1.一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物[ZnL(2,2′-bipy)(H2O)]n,其特征在于分子式为C18H12Br2N2O5Zn,分子量为561.49,该配合物以Zn2+为节点,L2-和2,2′-bipy为连接体相互连接,形成无限延续长的一维链状结构,链与链之间通过O-H···O分子氢键作用,有序堆积形成二维结构,属于单斜晶系,空间群为P21/c,晶胞参数为 α=90°,β=97.0940(10)°,γ=90°,Z=4,其晶体学数据见表1,部分和键角见表2,
表1.[ZnL(2,2′-bipy)(H2O)]n的晶体学数据
以上所述一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑锌配合物的制备方法,其特征在于具体步骤为:
(1)称量0.0575g ZnSO4·7H2O、0.0648g 2,5-二溴对苯二甲酸和0.0312g 2,2′-联吡啶溶于含有6mL N,N-二甲基甲酰胺和4mL蒸馏水的烧杯中,磁力搅拌30min,制得混合溶液;
(2)将步骤(1)制得的混合溶液转入25mL带有聚四氟乙烯瓶的反应釜中,放入烘箱加热至90℃,反应72h后,以10℃·h-1的速率降温至60℃,再保温2h,关闭烘箱让其在自然状态下冷却至室温后,取出反应釜,有无色透明块状晶体生成,即获得一种含溴侧链的对苯二甲酸与2,2′-联吡啶构筑的锌配合物。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103748064A (zh) * | 2011-08-17 | 2014-04-23 | 株式会社可乐丽 | 金属配合物以及由其制成的吸附材料、储藏材料和分离材料 |
JP2014169262A (ja) * | 2013-03-05 | 2014-09-18 | Nippon Steel & Sumitomo Metal | 多孔性高分子金属錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置 |
CN104368310A (zh) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | 一种强化甲烷吸附分离的金属有机骨架材料、制备及应用 |
CN107056824A (zh) * | 2017-04-24 | 2017-08-18 | 桂林理工大学 | 对苯二甲酸锌配合物的制备、结构及荧光性质 |
-
2020
- 2020-10-28 CN CN202011174410.XA patent/CN112961172A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103748064A (zh) * | 2011-08-17 | 2014-04-23 | 株式会社可乐丽 | 金属配合物以及由其制成的吸附材料、储藏材料和分离材料 |
JP2014169262A (ja) * | 2013-03-05 | 2014-09-18 | Nippon Steel & Sumitomo Metal | 多孔性高分子金属錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置 |
CN104368310A (zh) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | 一种强化甲烷吸附分离的金属有机骨架材料、制备及应用 |
CN107056824A (zh) * | 2017-04-24 | 2017-08-18 | 桂林理工大学 | 对苯二甲酸锌配合物的制备、结构及荧光性质 |
Non-Patent Citations (4)
Title |
---|
CCDC: "203465~203467(CCDC编号)检索结果", 《CCDC晶体数据库(HTTPS://WWW.CCDC.CAM.AC.UK)》 * |
ZHANG XINGHAO,等: "Coordination polymers driven by 2,5-dibromoterephthalic acid and chelating co-ligands: Syntheses, structures and luminescent properties", 《JOURNAL OF SOLID STATE CHEMISTRY 》 * |
张秀清,等: "吡唑羧酸类金属配合物的合成、晶体结构及其与牛血清白蛋白的相互作用", 《化学试剂》 * |
贾晓燕,等: "基于四氟对苯二甲酸为配体的两个锌(Ⅱ)的配合物的合成、晶体结构和荧光性质", 《无机化学学报》 * |
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