CN104628751B - 一种发光多孔配位聚合物及其制备方法和应用 - Google Patents
一种发光多孔配位聚合物及其制备方法和应用 Download PDFInfo
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Abstract
一种发光多孔配位聚合物及其制备和应用。本发明涉及的聚合物化学式为[Cd2(tba)3Cl],其中tba-1为配体4-(1,2,4-1H-三氮唑)苯甲酸的阴离子,该聚合物的晶体结晶为正交晶系,<i>Pnma</i>空间群,具有tba-1主配体和氯离子辅助配体桥联镉离子形成的一维孔道,其三维框架结构的孔洞率为37.5%。该聚合物采用溶剂热法制备。该聚合物可用于识别不同芳香分子的荧光探针,尤其是作为从芳香类分子中识别N,N-二甲基苯胺的分子荧光探针。本发明制备工艺简单,易实施,产物晶体纯度和产率均较高,且检测方法简单、选择性高,具有作为荧光探针及固体发光材料的良好前景。
Description
技术领域
本发明涉及多孔配位聚合物材料,尤其是发光多孔配位聚合物及其制备方法和应用。
背景技术
多孔配位聚合物是近年发展起来的一种新型的多孔材料,与传统的多孔材料如分子筛和活性炭相比,具有密度低、比表面积大、化学可修饰性强、结构柔性等优点,可广泛用于气体和液体的存储、分离、多相催化等领域(US 20100069234;US 20100282080;US20140061540;US 20130043407;WO/2010/090683A1;US 20080306315)。
最近几年,具有发光性能的多孔配位聚合物材料已经引起了人们的极大研究兴趣,这是因为该类化合物结合了发光性能和多孔吸附性能,以配位聚合物的骨架为“主体”,利用其内部的孔道来吸附具有特定性能的客体分子,使配位骨架与客体分子之间的产生“主客体”相互作用,进而达到影响或调控配合物发光性能的目的,成为一种新型的荧光探针,在光学传感器及发光器件等方面具有广泛的潜在应用(WO 2013137985;US20120040471 A1; CN 103822909A; Chem. Sci., 2011; J. Am. Chem. Soc. 2014,136, 7241)。然而,设计和构筑这类具有孔道结构且具有较好的发光性能的配位聚合物材料具有很大的挑战性。这是因为这类聚合物材料对于配体及金属的选择有严格的限制并且要求其有很好的稳定性。迄今为止,此类具有“主客体”相互作用调控的发光性能的材料的文献报道还相对较少,且大多报道在于识别离子、溶剂小分子、硝基苯和有机炸药等。例如,公开号CN102491988A “一种锌簇多孔发光配合物及其制备方法和应用” 提供了一种为含有多孔的三维网络结构,对铜、钡金属离子具有荧光增强或者淬灭效应而可作为荧光探针的配合物。程鹏等人利用镧系配位聚合物选择性荧光识别氟离子和有机小分子污染物如甲醛、乙腈和丙酮(Inorg. Chem. 2013, 52, 8082)等。Mukherjee小组和Zhang Qingfu等人利用由锌离子和有机配体构筑的多孔配位聚合物来识别硝基芳香化合物和有机爆炸物(Chem. Eur. J. 2014, 20, 4885;Chem. Eur. J. 2014, 20, 13321)。而公开号CN103588799A“一种镉配位聚合物”以包夹萘、菲、芘客体分子来实现“主体”发光性能的调控以作为能量转化器及固体发光材料的应用。
芳香类溶剂,如苯、甲苯、氯苯、硝基苯、苯胺、N-甲基苯胺、N,N-二甲基苯胺通常用作染料中间体,如香兰素、偶氮染料、三苯基甲烷染料,也可用作溶剂、稳定剂、分析试剂等。但芳香分子具有血液毒、神经毒和致癌性,能通过其蒸气或皮肤吸收引起中毒,抑制中枢神经和循环系统,引起头痛、衰弱、局部或全身缺氧、皮肤和黏膜发蓝、头昏和呼吸困难等,尤其是N,N-二甲基苯胺为剧毒物质,能使人呼吸短促而致死。尽管日本的Kitagawa小组研究了一个金属锌配位聚合物与N-甲基苯胺,N,N-二甲基苯胺及4-甲基-N,N-二甲基苯胺的主客体相互作用的荧光(Chem. Commun. 2007, 3142),然而目前利用该类材料从芳香类分子中识别N,N-二甲基苯胺的报道迄今尚属空白。探索与合成这类特殊的“主客体”相互作用的材料,对于理解和研究该类聚合物在配位结构上的普遍性质具有积极意义,开发这种新型的荧光探针或光学传感器等材料具有应用前景。
发明内容
本发明的目的在于针对现有技术所存在问题,提供一种发光多孔配位聚合物及其制备方法和应用,该镉配位聚合物可通过吸附不同的芳香客体分子实现对其发光性能的调控,以作为识别不同芳香分子的荧光探针,特别是可用于识别N,N-二甲基苯胺的分子荧光探针。
本发明的技术方案:
一种发光多孔配位聚合物:该聚合物化学式为[Cd2(tba)3Cl],其中,tba-1代表有机配体4-(1,2,4-1H-三氮唑)苯甲酸脱去质子后的阴离子;该聚合物具有tba-1配体和氯离子桥联镉离子形成的一维孔道,其三维框架结构的孔洞率为37.5%;该聚合物晶体属于正交晶系,空间群为Pnma,晶胞参数分别为:a = 25.786(5) Å、b = 21.045(4) Å、c = 7.4123(15) Å、α=β=γ=90o、V =4022.3(14) Å3;框架结构的分解温度为300oC。
制备上述的发光多孔配位聚合物的方法,包括以下步骤:
1)将4-(1,2,4-1H-三氮唑)苯甲酸和氯化镉加入到N,N-二甲基甲酰胺和甲醇组成的混合溶剂中混合均匀;
2)将上述所得混合液密封后在90~120 oC 下进行溶剂热反应,反应时间为48~72小时,以每小时5oC的速度冷却到室温,得到无色针状晶体;
3)用乙醚洗涤上述针状晶体,自然晾干,即制得该发光多孔配位聚合物的单晶样品;
4)120oC真空干燥,即可制得该发光多孔配位聚合物。
所述的多孔配位聚合物的制备方法中,步骤1)的4-(1,2,4-1H-三氮唑)苯甲酸和氯化镉的摩尔比为1:1~1:2。
所述的多孔配位聚合物的制备方法中,步骤1)的混合溶剂中N,N-二甲基甲酰胺和甲醇的体积比为3:1,而4-(1,2,4-1H-三氮唑)苯甲酸与混合溶剂的用量比为0.1毫摩尔:4毫升。
关于所述发光多孔配位聚合物的应用:以该聚合物作为识别芳香分子的荧光探针。
优选的,所述的多孔配位聚合物的应用:以该聚合物作为从芳香类分子中识别N,N-二甲基苯胺的分子荧光探针。
多孔配位聚合物的应用,其方法是将该多孔配位聚合物材料加入不同的芳香溶剂分子如苯、甲苯、氯苯、硝基苯、苯胺、N-甲基苯胺、N,N-二甲基苯胺中浸泡两天,即可得到一系列吸附不同客体的化合物材料。在紫外灯激发下,吸附苯、甲苯和氯苯的化合物材料发射蓝光,吸附硝基苯、苯胺、N-甲基苯胺的化合物材料呈现荧光淬灭,而吸附N,N-二甲基苯胺的化合物材料呈现很强的绿光发射。
本发明的优点是:该发光配位聚合物的配位骨架具有较高的热稳定性,可通过吸附不同的客体分子来实现对其发光性能的调控,其制备方法工艺简单、易于实施,晶体产率可达到50%以上,实验测得的粉末衍射图与理论模拟的基本吻合,证明其相纯度较高,可作为不同的芳香溶剂分子的荧光探针,特别是作为从芳香类分子中识别N,N-二甲基苯胺的分子荧光探针,并可作为固体发光材料,以期在材料科学领域具有良好的应用前景。
附图说明
图1为该发光多孔配位聚合物的配位结构图。
图2为该发光多孔配位聚合物的三维结构图。
图3为该发光多孔配位聚合物及单晶样品与单晶模拟的粉末衍射对比图。
图4为该发光多孔配位聚合物吸附不同的客体分子后的粉末衍射图。
图5为该发光多孔配位聚合物及单晶样品的热重曲线图。
图6为该发光多孔配位聚合物吸附不同的客体分子后在紫外线激发下的发光照片。
图7为该发光多孔配位聚合物吸附不同的客体分子后的荧光发射光谱。
具体实施方式
(一)制备发光多孔配位聚合物
实施例1:
将18.9毫克 (0.1毫摩尔)有机配体4-(1,2,4-1H-三氮唑)苯甲酸和22.8毫克(0.1毫摩尔)的CdCl2·2.5H2O加入到由3毫升N,N-二甲基甲酰胺 (DMF)和1毫升甲醇组成的混合溶剂中并混合均匀;所得混合液密封后在95 oC下进行溶剂热反应,反应48小时之后,以每小时5oC的速度冷却到室温,得到无色针状透明晶体,用乙醚洗涤,自然晾干,则制得该发光多孔配位聚合物的单晶样品,120oC真空烘干,即可制得该发光多孔配位聚合物。
实施例2:
将18.9毫克 (0.1毫摩尔)有机配体4-(1,2,4-1H-三氮唑)苯甲酸和45.6毫克(0.2毫摩尔)的CdCl2·2.5H2O加入到由3毫升N,N-二甲基甲酰胺 (DMF)和1毫升甲醇组成的混合溶剂中并混合均匀;所得混合液密封后在120 oC 下进行溶剂热反应,反应72小时之后,以每小时5oC的速度冷却至室温,得到无色针状透明晶体,用乙醚洗涤,自然晾干,则制得该发光多孔配位聚合物的单晶样品,120oC真空烘干,即可制得该发光多孔配位聚合物。
(二)多孔配位聚合物结构的测定
在显微镜下选取大小合适的单晶,温度T=293(2)K下在Rigaku R-AXIS SPIDER 衍射仪上,用经石墨单色器单色化的用Mo-K射线(λ= 0.71073Å),以ω-φ方式收集衍射数据。通过ABSCOR程序进行吸收校正。利用直接法使用SHELXTL程序解析和精修结构。先用差值函数法和最小二乘法确定全部非氢原子坐标,除了无序的N,N-二甲基甲酰胺(DMF)和水分子外,非氢原子坐标及各向异性参数进行全矩阵最小二乘法修正,再用理论加氢法得到主体骨架的氢原子位置,然后用最小二乘法对晶体结构进行精修。晶体学衍射点数据收集与结构精修的部分参数见下表1。
表1 :多孔配位聚合物晶体的参数表
化合物 | 1·0.5DMF·1.6H2O |
分子式 | C28.5H24.7Cd2ClN9.5O8.1 |
分子量 | 890.13 |
晶系 | 正交 |
空间群 | Pnma |
晶胞参数 | |
a (Å) | 25.786(5) |
b (Å) | 21.045(4) |
c (Å) | 7.4123(15) |
α (deg) | 90 |
β (deg) | 90 |
γ (deg) | 90 |
V (Å3 ) | 4022.3(14) |
Z | 4 |
理论密度(g cm-3) | 1.459 |
吸收系数(mm-1) | 1.176 |
F(000) | 1733 |
Rint | 0.0656 |
GOF | 1.122 |
R1 [I > 2σ (I)] | 0.0589 |
wR2 [all data] | 0.1483 |
图1、2为该配位聚合物的配位结构示意图,其中图1图中显示金属镉离子的配位模式,图2为该配位聚合物的三维结构图。
粉末衍射表征相纯度
粉末衍射数据收集在Rigaku D-MAX 2200 VPC衍射仪上完成,仪器操作电压40KV、电流35 mA,使用石墨单色化的铜靶X射线;在5o到40o范围内连续扫描完成,扫描速度为2o/每秒。单晶结构粉末衍射谱模拟转化使用Mercury 1.4.2。
图3为该多孔配位聚合物及单晶样品与单晶模拟的粉末衍射对比图,图中表明:所制得的多孔配位聚合物及单晶样品的衍射基本与单晶模拟的相一致,表明所制得的多孔配位聚合物样及单晶样品的纯度都比较高。
图4发光多孔配位聚合物吸附不同的客体分子后的粉末衍射图,从图中看出:吸附不同的客体分子后,所得到的样品与该多孔配位聚合物相比,其衍射峰位置基本吻合,这表明吸附客体后的化合物基本维持了原有的框架。
(三)发光多孔配位聚合物的热稳定性
发光多孔配位聚合物的热稳定性通过热重分析法检测。热重曲线是在氮气氛围中利用Netzsch STA 449C热分析仪上获得。热重曲线如图5所示,从图5可以看出制得的发光多孔配位聚合物及单晶样品的框架都可以稳定到300℃,根据失重量可以计算出该发光多孔配位聚合物单晶样品分子中包含0.5个N,N-二甲基甲酰胺(DMF)和1.6个水分子。
(四)客体依赖的荧光性能研究
将制备的该多孔配位聚合物分别浸泡在一系列的苯、甲苯、氯苯、硝基苯、苯胺、N-甲基苯胺以及N,N-二甲基苯胺溶液中两天后,过滤,真空干燥即可得到一系列吸附了不同客体的该化合物材料。
图6为该多孔配位聚合物吸附不同客体后在紫外线激发下的发光照片,图中显示:该配位聚合物在吸附客体后,在紫外光激发下也可以发出不同颜色的光。
荧光光谱实验使用日立公司(Hitachi)生产的F-4600荧光分光光度计完成。
图7为该多孔配位聚合物吸附客体后的荧光发射光谱,图中表明:吸附客体后,所得到的样品与该多孔配位聚合物相比,其荧光光谱发生了明显的红移,这表明该化合物的框架与客体分子之间发生了“主客体”相互作用。另外,该多孔配位聚合物吸附苯、甲苯和氯苯荧光增强,吸附硝基苯、N-甲基苯胺和N,N-二甲基苯胺荧光淬灭,而吸附N,N-二甲基苯胺发射出很强的绿色荧光,因此,该多孔配位聚合物可用于作为识别N,N-二甲基苯胺的荧光探针。
Claims (4)
1.一种发光多孔配位聚合物,其特征在于:该聚合物化学式为[Cd2(tba)3Cl],其中,tba-1代表有机配体4-(1,2,4-1H-三氮唑)苯甲酸脱去质子后的阴离子;该聚合物具有tba-1配体和氯离子桥联镉离子形成的一维孔道,其三维框架结构的孔洞率为37.5%;该聚合物晶体属于正交晶系,空间群为Pnma,晶胞参数分别为:a = 25.786(5) Å、b = 21.045(4) Å、c= 7.4123(15) Å、α=β=γ=90o、V =4022.3(14) Å3;框架结构的分解温度为300oC。
2.一种如权利要求1所述的发光多孔配位聚合物的制备方法,包括以下步骤:
1)将4-(1,2,4-1H-三氮唑)苯甲酸和氯化镉加入到N,N-二甲基甲酰胺和甲醇组成的混合溶剂中混合均匀;
所述步骤1)的4-(1,2,4-1H-三氮唑)苯甲酸和氯化镉的摩尔比为1:1~1:2;
所述步骤1)的混合溶剂中N,N-二甲基甲酰胺和甲醇的体积比为3:1,而4-(1,2,4-1H-三氮唑)苯甲酸与混合溶剂的用量比为0.1毫摩尔:4毫升;
2)将上述所得混合液密封后在90~120 oC 下进行溶剂热反应,反应时间为48~72小时,以每小时5oC的速度冷却到室温,得到无色针状晶体;
3)用乙醚洗涤上述针状晶体,自然晾干,即制得该发光多孔配位聚合物的单晶样品;
4)120oC真空干燥,即可制得该发光多孔配位聚合物。
3.一种如权利要求1所述的多孔配位聚合物的应用,其特征在于:将该多孔配位聚合物材料加入或苯或甲苯或氯苯或硝基苯或苯胺或N-甲基苯胺或N,N-二甲基苯胺之芳香溶剂分子中浸泡两天得到吸附不同客体的化合物材料,在紫外灯激发下,吸附苯、甲苯和氯苯的化合物材料发射蓝光,吸附硝基苯、苯胺、N-甲基苯胺的化合物材料呈现荧光淬灭,而吸附N,N-二甲基苯胺的化合物材料呈现很强的绿光发射。
4.根据权利要求3所述的多孔配位聚合物的应用,其特征在于:以该聚合物作为从芳香类分子中识别N,N-二甲基苯胺的分子荧光探针。
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