CN111732614A - 一种新型共晶钴配合物的合成方法 - Google Patents
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
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- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 3
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- 230000002194 synthesizing effect Effects 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 18
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- 238000004020 luminiscence type Methods 0.000 description 4
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- OONPLQJHBJXVBP-UHFFFAOYSA-N 3-(2-phenylethenyl)phthalic acid Chemical class OC(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1C(O)=O OONPLQJHBJXVBP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910020647 Co-O Inorganic materials 0.000 description 3
- 229910020676 Co—N Inorganic materials 0.000 description 3
- 229910020704 Co—O Inorganic materials 0.000 description 3
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Abstract
一种新型共晶钴配合物,属于三斜晶系,Pī空间群,所述新型共晶钴配合物的化学式为[Co(1,10‑phen)2(AcO)]·H2SDA·11H2O。将1,10‑邻菲罗啉和4,4′‑二苯乙烯二羧酸、氢氧化钠固体放入容积为30mL的聚四氟乙烯衬底水热反应釜中,加二甲基甲酰胺和水,搅拌后加入乙酸钴,调pH值后装入反应釜中恒温反应。过后取出反应釜放使其在室温下自然冷却再过滤留其滤液静置。室温条件下,经过三天的自然挥发结晶即可。其荧光性质研究结果表明,共晶钴配合物在低浓度时具有一定的荧光强度,具有良好的光致发光性能,且荧光强度随着溶液浓度的增大而逐渐减弱甚至猝灭,存在荧光浓度自猝灭效应。
Description
技术领域
本发明涉及一种配合物及其合成方法,具体是一种新型共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成方法。
背景技术
近年来,功能配合物的设计与合成因其独特的框架和拓扑结构以及在在催化,磁性,发光和气体吸收等领域的潜在应用而受到人们的广泛研究和关注。在功能配合物的合成中,有机配体的结构特征、金属离子的配位环境、抗衡阴离子、溶剂体系、反应温度以及体系的pH值等许多因素都会影响配合物的最终结构。因此,即使经过了多年的研究,功能配合物的结构也很难准确被预测。其中,金属离子的选择和有机配体的结构尤为重要,会直接影响配合物的结构及性质。相对于其他配体,芳香羧酸配体不仅具有羧酸配体配位模式多样化的特点,其特殊的骨架芳环结构易产生π···π堆积,羧酸中的氧原子还易于结构中的氢离子形成氢键,对所合成的金属-芳香羧基配合物结构及性能存在一定的影响。二苯乙烯二羧酸衍生物作为有机配体,在其羧基配位后,仍具有成氢键能力作为质子受体,苯环则为潜在的π-π作用位点,这些相互作用信息将被储存到所生成的配合物结构中,有可能对堆积结构的形成起导向作用。常用的刚性配体除了芳香羧酸外,氮杂环类刚性配体其骨架结构固定,在配位时不易发生变形,结构较易被控制,也被科研工作者们广泛应用于功能配合物的合成。
发明内容
本发明针对现有技术的不足,采用溶剂热法,以4,4'-二苯乙烯二羧酸和1,10-邻菲罗啉为配体,通过调控反应条件,构筑了一个新型的共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O,1,10-phen=1,10-邻菲罗啉,H2SDA=4,4'-二苯乙烯二羧酸,并对其晶体结构及荧光性质进行了研究。
为了实现上述目的,本发明采用了以下技术方案:
一种新型共晶钴配合物,所述新型共晶钴配合物的化学式为[Co(1,10-phen)2(AcO)]·H2SDA·11H2O,其中,1,10-phen=1,10-邻菲罗啉,H2SDA=4,4'-二苯乙烯二羧酸,所述新型共晶钴配合物的晶体学参数如表1所示,所述新型共晶钴配合物的部分键长和键角如表2所示,所述新型共晶钴配合物的氢键的键长和键角如表3所示。
与现有技术相比较,本发明具备的有益效果:
采用溶剂热法,以4,4'-二苯乙烯二羧酸和1,10-邻菲罗啉为定向配体,通过调节反应的原料摩尔比、反应溶剂、pH值、反应时间、反应温度等条件,成功构筑了一个新型的共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O。并通过IR、元素分析等方法对配合物的结构进行表征,并通过X-射线单晶衍射测定得到单晶结构。该共晶钴配合物的单晶结构中包含有一个由1,10-邻菲罗啉与乙酸钴配位形成的独立单核钴配合物和一个独立的4,4′-二苯乙烯二羧酸及11个游离的水分子。钴共晶配合物的荧光性质研究结果表明,共晶钴配合物在低浓度时具有一定的荧光强度,具有良好的光致发光性能,且荧光强度随着溶液浓度的增大而逐渐减弱甚至猝灭,存在荧光浓度自猝灭效应。
附图说明
图1为所述配合物的晶体结构。
图2为所述配合物的三维堆积图。
图3为所述配合物及配体的红外吸收光谱图。
图4为所述配合物的热重曲线图。
图5为所述配合物的荧光光谱图。
具体实施方式
下面通过实施例对本发明的技术方案作进一步阐述。
实施例1
1实验部分
1.1仪器和试剂
Agilent G8910ACCD单晶衍射仪;Perkin-Elmer 240Q元素分析仪;Bruker Vector22FT-IR型红外光谱仪;RF-5301PC型荧光光谱仪。所有试剂均为分析纯,均购自西陇化工股份有限公司。聚四氟乙烯衬底水热反应釜的安全温度是220度,最高压力为3Mpa,采用优质无磁性0Cr18Ni9Ti不锈钢精加工而成,内有聚四氟乙烯衬套,双层护理,可耐酸,碱等。1,10-邻菲罗啉的英文名称为1,10-phenanthroline,简称为菲咯啉、菲罗啉、菲啰啉,别称为1,10-邻菲啰啉、1,10-邻菲罗啉等。
1.2共晶配合物的合成
将1,10-邻菲罗啉(0.0991g,0.5mmol)和4,4′-二苯乙烯二羧酸(0.0671g,0.25mmol)、氢氧化钠固体(0.2000g,0.5mmol)放入容积为30mL的聚四氟乙烯衬底水热反应釜中,加入7mL二甲基甲酰胺(DMF)和8mL水,用磁力搅拌器搅拌1小时后加入乙酸钴(0.0443g,0.25mmol),再搅拌半小时后调pH值在10左右,继续搅拌30分钟后装入反应釜中放置在160℃电热鼓风干燥箱恒温反应3天。过后取出反应釜放使其在室温下自然冷却12小时再过滤留其滤液静置。室温条件下,经过三天的自然挥发结晶,滤液可获取红色的晶体[Co(1,10-phen)2(AcO)]·H2SDA·11H2O。
产量37.0mg,产率78.4%(以1,10-phen为基础计算)。
IRν:3435(O-H),1610(C=C),1426(C=C),1367(C-O),1226(C-O),826(C-H),779(C-H),716(C-H),526(Co-O),477(Co-N)cm-1。Anal.calcd for C42H53N4O17Co:C,53.39;H,5.65;N,5.93;found C,50.42;H,5.63;N,5.90。
1.3晶体结构解析
将测试样品(0.13mm×0.12mm×0.10mm)置于Agilent CCD单晶衍射仪上,用辐射于室温下以ω-2θ扫描方式采集数据,θ值的范围3.78≤θ≤27.28°(1),再用SADABS程序进行Lp因子校正和吸收校正,利用帕特森法确定金属离子的位置,后利用加氢理论求出氢原子坐标,最后利用最小二乘法对全部结构数据进行修正。计算过程均用SHELXS–97和SHLEXL–97及Olex2程序完成。
2结果与讨论
2.1晶体结构描述
表1所述配合物的晶体学参数表
表2配合物的部分键长和键角
表3配合物氢键的键长和键角
所述共晶钴配合物属于三斜晶系,Pī空间群,其晶体学参数、部分键长键角及氢键参数分别如表1、2和表3所示。从共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O(1,10-phen=1,10-邻菲罗啉,H2SDA=4,4′-二苯乙烯二羧酸)的晶体结构图1可以看出,结构中包含有一个独立的单核钴配合物和一个独立的4,4′-二苯乙烯二羧酸及11个水分子。这个共晶化合物包含1个单核钴配合物以及1个4,4′-二苯乙烯二羧酸和11个游离的水分子。由于结构中游离的这11个溶剂水分子与主体结构没有较强的键合作用,处于无序状态,导致晶体参数中的wR2值偏大。在独立的单核钴配合物结构中,可以基于常规的Co-O和Co-N键的键长和分子电中性原理可以得出钴离子的化合价为+2。Co(Ⅱ)处于六配位的配位环境,它分别与来自两个1,10-邻菲罗啉环上的四个氮原子 与一个乙酸上两个氧原子 进行配位。N(1)、N(3)、N(4)、O(1)构成了八面体的赤道平面,0.4828x-0.3718y-0.7929z=-6.0645是最佳二乘平面方程,赤道平面上的四个原子平均偏离O(2)与N(2)是八面体的两个顶点,到平面的距离分别是Co(Ⅱ)偏离该平面的距离为使其形成扭曲的CoN4O2八面体构型。共晶结构中,水分子间以及溶剂水分子与二苯乙烯二羧酸配体的氧原子之间存在O–H···O氢键作用,如结构图所示,具体氢键参数如表3所示。其三维堆积图如图3所示,在配合物中,配合物1的一维链状通过分子间1,10-邻菲罗啉环的π···π作用堆积形成二维平面结构,相邻层的链是平行的,其二维结构进一步通过结构中另一个1,10-邻菲罗啉环的分子间π···π作用穿插堆积形成三维结构,如图2所示。
2.2配合物的红外光谱分析
配合物的红外吸收光谱如图3所示,3435cm–1是游离水分子的O-H伸缩振动峰,1610cm–1、1426cm–1为苯环骨架C=C伸缩振动的特征峰,1367cm–1和1226cm–1是C-O伸缩振动峰,826cm–1是苯环C-H键的变形振动峰,779cm-1和716cm–1为吡啶环上的C-H外弯曲振动峰。526cm–1和477cm–1分别是Co-O、Co-N的伸缩振动峰,表明了钴离子参与了配位。
2.3热稳定性
配合物的热分析TGA曲线如图4,该分析在氮气气体下,升温速率具体为10℃/min的条件下进行。热重分析表明,标题配合物在45~220℃之间失重率是19.8%,失去的是晶体结构中的11个游离溶剂水分子;随着温度的升高,配合物继续失重,在225~410℃之间失重率为25%,失去的是共晶H2SDA配体。当温度高于410℃,配合物骨架结构不稳定,开始出现分解,在410~600℃之间失重率为21%,失去的是参与配位的一个1,10-邻菲罗啉配体,在600~700℃之间失重率为28%,是配合物骨架继续分解,先后失去另一个配位的1,10-邻菲罗啉配体和乙酸根。最后的残留物可能是金属氧化物CoO。
2.4荧光性质
在365nm紫外灯照射下,一定浓度的配合物DMF溶液(1×10-5mol/L)发射出一定的荧光,显示了目标配合物具有一定的发光性能,且其荧光强度强于配体1,10-邻菲罗啉和4,4′-二苯乙烯二羧酸。配体和配合物的这种发光方式归属于配体内部的π→π*电子跃迁。而配合物的发光强度更强是因为配体在配位后,结构的刚性得到增强,激发后通过振动松弛消耗的能量比例降低。同时,分别测定了浓度为5×10-5mol/L、1×10-5mol/L、5×10-6mol/L、1×10-6mol/L、5×10-7mol/L的共晶配合物DMF溶液的荧光光谱,探究浓度对其荧光强度的影响。如图5,共晶化合物的荧光强度随着溶液浓度的增加而显著减弱,表明其存在荧光自猝灭效应。
Claims (5)
2.一种新型共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成方法,其特征在于,
(一)反应所需试剂及其用量
以1,10-邻菲罗啉、4,4′-二苯乙烯二羧酸、氢氧化钠和乙酸钴为反应物,
所述1,10-邻菲罗啉、4,4′-二苯乙烯二羧酸、氢氧化钠和乙酸钴的物质的量之比为1.8~2.2:0.8~1.2:1.8~2.2:0.8~1.2;
以DMF和水为溶剂,
DMF的用量按照每0.5mmol的1,10-邻菲罗啉加入6.5~7.5mL的DMF计算,
水的用量按照每0.5mmol的1,10-邻菲罗啉加入7.5~8.5mL的水计算;
(二)合成反应的操作步骤
(1)按照(一)中所述的比例称取各个反应物备用,按照(一)中所述的比例量取溶剂备用;
(2)将步骤(1)所述1,10-邻菲罗啉、4,4′-二苯乙烯二羧酸和氢氧化钠放入反应釜中;
(3)向反应釜中加入步骤(1)所述DMF和水,搅拌均匀;
(4)向反应釜中加入步骤(1)所述乙酸钴,搅拌均匀;
(5)调节反应体系的pH值至9.5~10.5,搅拌均匀;
(6)将反应釜放置在150~170℃干燥箱中恒温反应至结束;
(7)将反应釜从干燥箱中取出并放置在室温下自然冷却,再过滤取滤液;
(8)室温下,滤液自然挥发结晶得到的晶体即为[Co(1,10-phen)2(AcO)]·H2SDA·11H2O。
3.如权利要求2所述的新型共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成方法,其特征在于,所述的反应釜为聚四氟乙烯衬底水热反应釜。
4.如权利要求2所述的新型共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成方法,其特征在于,步骤(4)中用氢氧化钠溶液调节pH值。
5.如权利要求2所述的新型共晶钴配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成方法,其特征在于,所述1,10-邻菲罗啉、4,4′-二苯乙烯二羧酸、氢氧化钠和乙酸钴的物质的量之比为2:1:2:1。
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