CN112521409B - 一种锌配合物及其应用 - Google Patents
一种锌配合物及其应用 Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 35
- -1 2, 5-bis (methylthio) -1, 4-phenylene Chemical group 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 13
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- ZTNZXZISERUKOK-UHFFFAOYSA-N 4-[2,5-bis(methylsulfanyl)-4-pyridin-4-ylphenyl]pyridine Chemical compound CSc1cc(c(SC)cc1-c1ccncc1)-c1ccncc1 ZTNZXZISERUKOK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及材料技术领域，具体涉及一种锌配合物及其应用。具体技术方案为：一种锌配合物，其化学式为{[Zn(L)(OBA)]}n，其中L为4,4’‑(2,5‑二(甲硫基)‑1,4‑亚苯基)二吡啶，OBA2‑为4,4'‑二苯醚二甲酸离子，可用于检测废水中的Fe3+。本发明通过4,4’‑(2,5‑二(甲硫基)‑1,4‑亚苯基)二吡啶配体和4,4'‑二苯醚二甲酸与Zn(II)离子组装，合成了一个结构新颖的配合物{[Zn(L)(OBA)]}n。
Description
技术领域
本发明涉及材料技术领域，具体涉及一种锌配合物及其应用。
背景技术
金属配位聚合物一般是由作为配位中心的金属原子和有机配体自组装得到的一类新型晶态材料。金属离子(金属团簇)与有机配体之间的有规律的排列，产生的骨架结构拥有多种多样的性质。近年来在选择性催化、气体吸附分离、荧光传感、分子识别、磁性分子材料以及生物医药等领域显示出广阔的应用前景，成为化学工作者的研究热点。
金属离子对生物生长和自然环境有着重大的影响，因此近年来生物体和环境中金属离子的检测引起了很大的关注。和传统的检测金属离子方法(拉曼光谱、离子淌度谱、气相色谱)相比，利用MOFs来检测具有低廉、易合成、电子可调、易操作等特点。因此，本发明合成了一种新的金属配合物用于检测金属离子。
发明内容
针对现有技术的不足，本发明提供了一种锌配合物，通过4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶配体和4,4'-二苯醚二甲酸与Zn(II)离子组装，合成了一个结构新颖的配合物{[Zn(L)(OBA)]}n。
为实现以上目的，本发明通过以下技术方案予以实现：
本发明公开了一种锌配合物，其化学式为{[Zn(L)(OBA)]}n，其中L为4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶，OBA2-为4,4'-二苯醚二甲酸离子。
相应的，一种锌配合物，其分子式为C32H28ZnN2O5S2。
优选的，所述锌配合物为单斜晶系，空间群为C2/c空间群，晶胞参数为a＝2.5265(2)nm，α＝90.00°；b＝1.4623(1)nm，β＝97.37(2)°；c＝1.7159(1)nm，γ＝90.00°，V＝6.2869(3)nm3。
优选的，所述锌配合物单晶体结构中，最小不对称单元中包含晶体学独立锌离子、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶配体和完全质子化的4,4'-二苯醚二甲酸离子。
相应的，一种锌配合物的制备方法，将Zn(NO3)2·6H2O、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和4,4'-二苯醚二甲酸溶于DMF水溶液中，反应完成后，冷却至室温，即得到锌配合物。
优选的，所述Zn(NO3)2·6H2O、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和4,4'-二苯醚二甲酸的摩尔比为0.5～2:0.5～2:0.5～2。
优选的，反应温度为80～100℃，时间为60～80h。
优选的，所述DMF水溶液中DMF和水的体积比为0.5～1.5:0.5～1.5。
相应的，一种锌配合物在检测Fe3+上的应用。
优选的，所述Fe3+的检测浓度为1.0×10-6mol/L。
本发明具备以下有益效果：
本发明采用水热法，将硝酸锌、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶(L)和4,4'-二苯醚二甲酸(H2OBA)混合，生成了一种三维配合物{[Zn(L)(OBA)]}n，并对其进行了结构分析和表征。其中，锌离子分别与4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和质子化的4,4'-二苯醚二甲酸连接形成两条一维链，这两条一维链又相互连接形成三维结构。经过荧光测试表明，配合物对Fe3+显示出明显的荧光猝灭现象，猝灭常数为2.983×104M-1。因此，本发明公开的锌配合物对检测废水中的Fe3+具有潜在的应用价值。
附图说明
图1为锌配合物的分子结构图；
图2为锌配合物的三维结构图；
图3为锌配合物的热重曲线；
图4为锌配合物的XRD图谱；
图5为锌配合物和配体L的固体荧光曲线；
图6为锌配合物在不同硝酸盐水溶液中的荧光强度；
图7为锌配合物在水中随着Fe3+(1mM/L)的滴加而荧光猝灭曲线；
图8为Fe3+的S-V曲线。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
若未特别指明，实施举例中所用的技术手段为本领域技术人员所熟知的常规手段。
本发明中，Zn(NO3)2·6H2O，DMF(二甲基甲酰胺)，4,4'-二苯醚二甲酸均为分析纯，使用前未进一步纯化；4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶根据现有技术合成；实验水为超纯水。
1.本发明公开了一种锌配合物，其化学式为{[Zn(L)(OBA)]}n，其中L为4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶，OBA2-为4,4'-二苯醚二甲酸离子。
2.本发明公开了一种锌配合物的合成方法，将Zn(NO3)2·6H2O、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和4,4'-二苯醚二甲酸溶于DMF水溶液中，反应完成后，冷却至室温，即得到无色透明的块状晶体-锌配合物。其中，Zn(NO3)2·6H2O、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和4,4'-二苯醚二甲酸的摩尔比为0.5～2:0.5～2:0.5～2。反应温度为80～100℃，时间为60～80h。DMF水溶液中DMF和水的体积比为0.5～1.5:0.5～1.5。
下面结合具体的实施例对本发明进行进一步的阐述。
实施例1锌配合物的制备
将Zn(NO3)2·6H2O(29.7mg，0.1mmol)，4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶(32.2mg,0.1mmol)，4,4'-二苯醚二甲酸(25.8mg，0.1mmol)溶于6mL的DMF和H2O混合溶液中，其中DMF和水的体积比为1:1，将溶液转移至20mL聚四氟乙烯内衬的不锈钢反应釜中，在95℃下反应72h，自然冷却至室温后，得到无色透明的块状晶体，产率为47％。
元素分析理论值(％，C32H28ZnN2O5S2，Mr＝650.09):C 27.58，H 1.59，N 5.25；实测值(％)：C 27.50，H 1.64，N 5.17。配合物红外吸收峰(KBr固体压片ν/cm-1)：3508(s,br),1647(s),1525(s),1385(m),1207(m),780(m),657(m)，580(m)。
实施例2配合物晶体结构的测定
选取尺寸合适且透明度好的由实施例1制备的无色块状晶体，置于Bruker SmartApex II CCD单晶衍射仪上，用经石墨单色化的Mo-Ka(λ＝0.071073nm)辐射为光源对晶体进行扫描并收集X-射线单晶衍射点，收集的数据通过SADAB程序做吸收校正，采用SHELXT程序直接法解出。所有碳上的氢原子均根据理论加氢获得，并对氢原子和非氢原子分别采用各向同性和各项异性温度因子进行全矩阵最小二乘法修正。配合物的晶体学数据见表1，部分键长和键角见表2。
表1配合物的晶体学数据和精修参数
表2配合物的主要键长(nm)和键角(°)
对称中心:#1:-1/2+x,3/2-y,-1/2+z。
结果显示，配合物{[Zn(L)(OBA)]}n属于单斜晶系，C2/c空间群。X-射线单晶体结构表明，其最小不对称单元中包含一个晶体学独立的Zn(II)离子，一个L配体，一个完全质子化的4,4'-二苯醚二甲酸离子。
如图1所示，Zn(II)是属于四配位的构型，其中的两个O原子来自两个OBA2-离子，两个N原子来自两个不同的L配体，最终形成一个扭曲的四面体结构。Zn-O键的距离是0.1962(6)和0.1968(5)nm，Zn-N键的距离是0.2055(5)和0.2078(6)nm。
如图2所示，Zn(II)离子与L配体连接形成一个一维Z字型的链，Z字型的链和Zn(II)离子与OBA2-离子所形成的另外一条波浪型一维链连接，形成三维结构。
实施例3配合物{[Zn(L)(OBA)]}n的热重分析和粉末X射线衍射分析
为了表征锌配合物的热稳定性，对其进行热重表征。如图3所示，锌配合物能够稳定到350℃，然后随着配体的分解主体结构开始坍塌。
图4为配合物{[Zn(L)(OBA)]}n的粉末X-射线图谱(PXRD)，通过与单晶模拟的PXRD图谱对照可以发现，实验衍射谱图和模拟的谱图吻合的很好，证实了合成的配合物是均一的纯相。
实施例4配合物的固体荧光性能
在室温下研究了配体L和配合物{[Zn(L)(OBA)]}n的固体荧光性能。如图5所示，配合物的固体荧光的最大发射波长在460nm处，而配体L的最大发射波长为430nm处。配合物的发射波长较配体L红移了大约30nm，可以认为配合物的发光是来自于配体L之间的电子转移。
实施例5配合物对Fe3+的荧光传感研究
由于配合物{[Zn(L)(OBA)]}n具有较强的荧光发射和热稳定性，因此能够被用作荧光探针来探测阳离子。将2mg研磨好的配合物置于2mL的1mM/L的金属硝酸盐的DMF溶液并记录荧光曲线。如图6所示，不同的金属离子对配合物的荧光强度都有不同程度的影响，而配合物的荧光在Fe3+水溶液中几乎全部猝灭，可见配合物和铁离子之间的电子转移造成了配合物的荧光猝灭。
对于Fe3+能猝灭配合物的荧光的现象，进一步做了荧光滴定实验。取2mg研磨成粉末的配合物置于2mL水中，超声30min形成悬浮液后，再静置5h，然后将悬浮液转移至比色皿中。如图7所示，随着1mM/L的Fe3+的不断加入，配合物的荧光强度逐渐降低，当Fe3+的滴加量达到80μL时，荧光强度仅为原来的9.0％。荧光猝灭常数可通过Stern-Volmer(S-V)方程：I0/I＝1+Ksv[Q]得到，其中Ksv是荧光猝灭常数，[Q]是Fe3+的浓度，I0和I分别是配合物起始和加入Fe3+后悬浮液的荧光强度。由图8可以看到，在低浓度范围内，配合物的S-V曲线呈线性关系，计算得到Ksv为2.983×104M-1，并且当Fe3+的浓度仅为1.0×10-6mol/L时就可以检测出来，显示出极高的灵敏度，对检测废水中的Fe3+具有潜在的应用价值。
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (6)
1.一种锌配合物，其特征在于：其化学式为{[Zn(L)(OBA)]}n，其中L为4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶，OBA2-为4,4'-二苯醚二甲酸离子；
所述锌配合物为单斜晶系，空间群为C2/c空间群，晶胞参数为a＝2.5265(2)nm，α＝90.00°；b＝1.4623(1)nm，β＝97.37(2)°；c＝1.7159(1)nm，γ＝90.00°，V＝6.2869(3)nm3；
所述锌配合物单晶体结构中，最小不对称单元中包含晶体学独立锌离子、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶配体和完全质子化的4,4'-二苯醚二甲酸离子。
2.根据权利要求1所述的一种锌配合物，其特征在于：其分子式为C32H28ZnN2O5S2。
3.一种权利要求1或2所述的锌配合物的制备方法，其特征在于：将Zn(NO3)2·6H2O、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和4,4'-二苯醚二甲酸溶于DMF水溶液中，反应完成后，冷却至室温，即得到锌配合物；所述Zn(NO3)2·6H2O、4,4’-(2,5-二(甲硫基)-1,4-亚苯基)二吡啶和4,4'-二苯醚二甲酸的摩尔比为0.5～2:0.5～2:0.5～2。
4.根据权利要求3所述的一种锌配合物的制备方法，其特征在于：反应温度为80～100℃，时间为60～80h。
5.根据权利要求3所述的一种锌配合物的制备方法，其特征在于：所述DMF水溶液中DMF和水的体积比为0.5～1.5:0.5～1.5。
6.一种权利要求1～2任一项所述的锌配合物或权利要求3～5任一项所述制备方法制备的锌配合物在检测Fe3+上的应用，其特征在于：所述Fe3+的检测浓度为1.0×10-6mol/L。
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