CN108409758B - 含双核稀土簇合物的晶态材料及其制备方法和应用 - Google Patents
含双核稀土簇合物的晶态材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及采用4‑碘‑3‑甲基苯甲酸(IMBA)与稀土盐反应,采用溶剂热法,一锅法合成了双核稀土簇合物的晶态材料。制备方法步骤如下:a)将LnmXn(Ln=三价稀土离子)溶解于溶液中备用;b)将脱质子的4‑碘‑3‑甲基苯甲酸溶液加入到a)溶液中;c)将4,7‑二甲基‑1,10‑菲啰啉(dmp)溶解于乙醇溶剂中,然后加入到a)溶液中;d)将以上混合溶液置于60℃烘箱中,一段时间后能看到无色块状晶体析出;e)将上一步得到的无色块状透明晶体过滤晾干。该方法操作简便,设计合理,操作简单,快捷,且无需贵重的仪器设备,具有很强的创造性和实用性。并且,所述的双核稀土簇合物的晶态材料可以便捷的检测Fe2+以及乙醚溶剂分子。
Description
技术领域
本发明涉及含双核稀土簇合物以及快速检测Fe2+和乙醚溶剂分子的技术领域,具体涉及利用溶剂热法合成含双核簇合物的晶态材料的制备方法以及对Fe2+和乙醚溶剂分子的检测与分析。
背景技术
近年来科技发展趋势显示,单一功能的材料已经不能满足人们的实际应用的要求,因此,多功能材料已经成为材料领域的热门研究之一。稀土有机-无机杂化材料的研究经历了从单一功能的杂化材料向多功能杂化材料转变的发展过程。稀土配位聚合物光致发光的研究始于20世纪40年代[108],最初主要研究的对象是Tb3+和Eu3+的可见发光。因其稀土离子近红外发光在诊断学、激光系统、光纤通信及荧光免疫分析等领域的应用有着特殊的优点,所以,随着检测技术的不断发展,稀土Pr3+、Nd3+、Sm3+、Dy3+、Ho3+、Er3+、Tm3+和Yb3+配合物的近红外发光也被深入研究。
稀土元素共有17个,包含从原子序数57的镧(La)到71的镥(Lu)15种元素,加上位于同一ⅢB族的原子序数为21的钪(Sc)和原子序数为39的钇(Y)。其中铽为位于元素周期表第65位,外层电子结构为[Xe]4f96s2。铽与其它稀土元素外层电子结构相同,内层的4f电子能级相近,使铽与其它稀土元素表现出许多相似的物理和化学性质,例如:高配位性、光致发光、光电转化、磁性等性质,因而在催化、光、电、磁等领域具有广泛的应用。稀土簇合物是稀土离子与有机配体通过配位键连接形成的高度规整的、具有一定重复结构单元的化合物,所以,簇合物的设计与合成是无机化学研究的重要内容。
含双核的金属簇合物检测亚铁离子已有报道,但是,尚未发现同时检测亚铁离子以及乙醚溶剂分子的含双核的金属簇合物的报道。
发明内容
本发明的目的在于提供一种含双核稀土簇合物的晶态材料及其制备方法,并且提供利用含双核稀土簇合物的晶态材料检测Fe2+或乙醚溶剂分子的方法。
为达到上述目的,本发明采用以下技术方案:
一种含双核稀土簇合物的晶态材料,其特征在于:由稀土(III)元素、配体4-碘-3-甲基苯甲酸以及辅助配体4,7-二甲基-1,10-菲啰啉构筑,含双核稀土簇合物的晶态材料的分子式为[Ln2C76H60I6N4O12]n(Ln=稀土离子);所述稀土簇合物晶体中的Ln(III)簇合物结晶于单斜晶系P-1空间群:晶胞参数是 α=64.098(3)°~65.971(3)°,β=79.173(2)°~81.262(2)°,γ=61.393(2)°~63.461(4)°,Z=2。
优选的,所述的稀土(III)元素为Eu(III)、Tb(III)或Gd(III)。
本发明中的含双核稀土簇合物的晶态材料是通过含羧酸芳香烃构筑得到的,具体为稀土元素(III)和配体4-碘-3-甲基苯甲酸以及辅助配体4,7-二甲基-1,10-菲啰啉构筑的三维聚合物。该方法包括如下步骤:
(a)将LnmXn溶解于溶剂中备用,上式中Ln为三价稀土离子,X为阴离子,m和n为正整数;
(b)将脱质子的4-碘-3-甲基苯甲酸溶液加入步骤(a)中的溶液中;
(c)将4,7-二甲基-1,10-菲啰啉溶解于乙醇溶剂中,然后加入到步骤(a)中的溶液中;
(d)将以上混合溶液加热到60℃并保持一段时间,得到块状无色透明单晶;
(e)将上一步得到的块状无色透明单晶过滤晾干,即得到含双核稀土簇合物的晶态材料。
优选的,所述的溶解LnmXn的溶剂为水或/和有机溶剂。更优选的,所述的有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、甲醇、乙醇、乙腈、丙酮、乙酰丙酮、二氯甲烷和三氯甲烷中的至少一种。
优选的,所述的X为硝酸根、卤素离子、磺酸根、草酸根、醋酸根和三氟甲磺酸根中的一种。
本发明中的含双核簇合物晶态材料对亚铁离子以及乙醚溶剂分子具有快速灵敏的检测效果,所以可以用于检测亚铁离子或乙醚溶剂分子。
本发明与现有技术相比具有的有益效果:本发明通过溶剂热法合成了含双核的系列稀土簇合物,合成的Eu(III)簇合物既对乙醚溶剂分子具有灵敏的检测效果,同时对亚铁离子具有快速灵敏的检测效果,合成的Tb(III)簇合物对亚铁离子具有快速灵敏的检测效果,方法简单易行,操作简单,无需贵重精密仪器设备,且制备含核稀土簇合物单晶的方法简便,无需贵重的仪器设备。
附图说明
图1、本发明所合成的Eu(III)簇合物与11种不同的溶剂分子反应24h后的归一化强度柱状图三维荧光图。
图2、本发明所合成的Eu(III)簇合物与十二种金属离子以及人体必需的八种氨基酸溶液反应1h的紫外吸收图和对应样品示意图。
图3、本发明所合成的Tb(III)簇合物与十二种金属离子以及人体必需的八种氨基酸溶液反应1h的紫外吸收图和对应样品示意图。
图4、本发明所合成的Eu(III)簇合物的结构单元示意图(为了清晰起见,所有氢原子均删去)。
图5、本发明所合成的Eu(III)簇合物的双核簇结构示意图。
图6、本发明所合成的Eu(III)簇合物中配体的配位模式示意图。
具体实施方式
下面结合实施例对本发明做进一步的说明,但并不局限于下述实施例。
含双核的系列稀土簇合物的晶态材料的制备及其晶体结构。
实施例1:Tb(III)簇合物的制备
(1)将13.22mg 4-碘-3-甲基苯甲酸置于烧杯中,加入10mL水,并用0.1M氢氧化钠溶液调节pH为6,得溶液A;
(2)将15.0mg六水合硝酸铽与10mL丙酮混合,得溶液B;将上述的溶液A缓慢滴加到溶液B中,得混合液C;
(3)将7.0mg 4,7-二甲基-1,10-菲啰啉溶解于2mL乙醇中,得溶液D;
(4)将混合液C和溶液D混合,所得混合液置于60℃烘箱中,五天后得到无色透明的块状晶体Tb(III)配位聚合物I,即含双核的簇合物晶态材料。
实施例2:Eu(III)簇合物的制备
(1)将13.22mg 4-碘-3-甲基苯甲酸置于烧杯中,加入10mL水,并用0.1M氢氧化钠溶液调节pH为6,得溶液A;
(2)将15.0mg六水合硝酸铕与10mL丙酮混合,得溶液B;将上述的溶液A缓慢滴加到溶液B中,得混合液C;
(3)将7.0mg 4,7-二甲基-1,10-菲啰啉溶解于2mL乙醇中,得溶液D;
(4)将混合液C和溶液D混合,所得混合液置于60℃烘箱中,五天后得到无色透明的块状晶体Eu(III)配位聚合物Ⅱ,即含双核的簇合物晶态材料。
实施例3:Gd(III)簇合物的制备
(1)将13.22mg 4-碘-3-甲基苯甲酸置于烧杯中,加入10mL水,并用0.1M氢氧化钠溶液调节pH为6,得溶液A;
(2)将15.0mg六水合硝酸钆与10mL丙酮混合,得溶液B;将上述的溶液A缓慢滴加到溶液B中,得混合液C;
(3)将7.0mg 4,7-二甲基-1,10-菲啰啉溶解于2mL乙醇中,得溶液D;
(4)将混合液C和溶液D混合,所得混合液置于60℃烘箱中,五天后得到无色透明的块状晶体Gd(III)配位聚合物Ⅲ,即含双核的簇合物晶态材料。
上述三个实施例中的稀土配位聚合物Ⅰ、Ⅱ、Ⅲ为异质同晶结构。
单晶结构分析表明稀土配位聚合物I、II和Ⅲ均结晶于单斜晶系P-1空间群,稀土配位聚合物I晶胞参数是α=65.098(3)°,β=80.207(3)°,γ=62.461(4)°,Z=2;稀土配位聚合物II晶胞参数是 α=65.271(3)°,β=80.262(2)°,γ=62.424(2)°,Z=2;稀土配位聚合物Ⅲ晶胞参数是 α=65.140(2)°,β=80.173(2)°,γ=62.393(2)°,Z=2。其分子式为[Ln2C76H60I6N4O12]n(Ln=稀土离子)。由于稀土配位聚合物Ⅰ、Ⅱ、Ⅲ是异质同晶结构,我们以稀土配位聚合物Ⅱ为例描述他们的结构。通过结构分析可知Ⅱ是双核结构的稀土配合物,结晶于三斜晶系,P-1空间群,晶胞参数为 α=65.271(3)°,β=80.262(2)°,γ=62.424(2)°,Z=2。Ⅱ的双核结构如图4,两个金属中心和六分子IMBA以及两分子dmp配位组成一个中性的配位单元双核结构中的Eu1和Eu2均采取八配位模式(图4b和c),其中六个O来自于三个羧酸,两个N来自于配体dmp,金属周围的八个配位原子均采取扭曲的双冒三棱柱模式排布。该双核簇结构是由两个非等价的Eu3+由四个羧基桥连而形成双核团簇结构(图5)。配体IMBA的羧酸基团采取螯合和桥连两种配位模式(图5)。Eu-O的键长位于之间,Eu-N的键长位于之间。
实施例4:Eu(III)簇合物用于检测乙醚溶剂分子
分别取乙酰丙酮、乙醇、二氯甲烷、四氢呋喃、乙腈、苯、甲醇、丙酮、正己烷、DMF、乙醚等溶剂各10mL,然后每种溶剂分别加入10mg的Eu(III)簇合物,摇匀后静置反应24小时后测量其荧光强度,如图1所示,柱状图清楚地表明,尽管Eu(III)簇合物在大多数溶剂中的荧光强度比较相似,但在Et2O显示了非常弱的荧光发射。结果表明Eu(III)簇合物具有对Et2O溶剂分子的灵敏检测作用。
实施例5:Eu(III)簇合物用于检测亚铁离子
分别配制10-3M的十二种金属离子溶液(MClx,M=Ba2+,Ca2+,Cd2+,Co3+,Cr3+,Fe2+,K+,Mg2+,Mn2+,Pb2+,Zn2+,Ni2+)以及10-3M的人体必需的八种氨基酸溶液(Leu,Lys,Phe,Met,Trp,Val,Ile,Thr)作为储备液。然后用DMF作为溶剂配制10-3M的Eu(III)簇合物溶液。依次分别取上述20种不同储备液0.05mL加入到20个不同的小瓶中,依次编号1-20。然后向20个小瓶中分别加入4.90mL的去离子水以及0.05mL的Eu(III)簇合物溶液,此时形成含有10μMEu(III)簇合物,10μM金属离子或氨基酸的5mL混合溶液。另取一小瓶编号21,然后分别加入4.95mL的去离子水以及0.05mL的Eu(III)簇合物溶液。摇匀上述的21个小瓶的溶液,发现含有Fe2+的混合溶液的颜色立即由无色变为浅红色。之后,将混合溶液置于室温下反应1小时,然后进行紫外分光光度测试。紫外可见吸收光谱表明Eu(III)簇合物当与FeCl2反应后有明显的紫外吸收增强(如图2a)所示)。在图2b)中,随着样品Eu(III)簇合物浓度的增加(FeCl2浓度不变),紫外吸收增强逐渐增加。同时,FeCl2浓度为10-6M时,b浓度固定,仍有紫外吸收增强(约510nm)。同时,当样品Eu(III)簇合物浓度不变时,FeCl2浓度为10-6M时,仍有紫外吸收增强(约510nm处)。当FeCl2的浓度达到10-7M时,没有观察到紫外吸收增强,如图2c)所示。结果表明,样品Eu(III)簇合物用于检测Fe2+的最低浓度为1.0×10-6M(0.127mg·L-1),具有灵敏的检测效果。
实施例6:Tb(III)簇合物用于检测乙醚溶剂分子或亚铁离子
如图3所示,使用上述方法,Tb(III)簇合物代替Eu(III)簇合物时,发现Tb(III)簇合物对FeCl2溶液同样有显色反应,而对其它金属离子或氨基酸溶液没有显色反应,说明Tb(III)簇合物对FeCl2溶液具有专一的检测效果。进一步实验结果表明,样品Tb(III)簇合物用于检测Fe2+的最低浓度为1.0×10-6M(0.127mg·L-1),具有灵敏的检测效果(如图3c)所示)。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种含双核稀土簇合物的晶态材料,其特征在于:由稀土(III)元素、配体4-碘-3-甲基苯甲酸以及辅助配体4,7-二甲基-1,10-菲啰啉构筑,含双核稀土簇合物的晶态材料的分子式为[Ln2C76H60I6N4O12]n,其中Ln = 稀土离子;所述含双核稀土簇合物的晶态材料结晶于单斜晶系P-1空间群:晶胞参数是a = 16.0716(7) Å~16.7862(4) Å,b = 16.1358(6) Å~17.6991(4) Å,c = 17.0384(6) Å~18.2775(4) Å,α = 64.098(3)°~65.971(3)°,β =79.173(2)°~81.262(2)°,γ = 61.393(2)°~63.461(4)°,V = 3717.8(3) Å3~4334.13(16)Å3,Z = 2;所述的稀土(III)元素为Eu(III)或Tb(III)。
2.根据权利要求1所述的含双核稀土簇合物的晶态材料的制备方法,包括如下步骤:
(a)将LnmXn溶解于溶剂中备用,上式中Ln为三价稀土离子,X为阴离子,m和n为正整数;
(b)将脱质子的4-碘-3-甲基苯甲酸溶液加入步骤(a)中的溶液中;
(c)将4,7-二甲基-1,10-菲啰啉溶解于乙醇溶剂中,然后加入到步骤(a)中的溶液中;
(d)将以上混合溶液加热到60℃并保持一段时间,得到块状无色透明单晶;
(e)将上一步得到的块状无色透明单晶过滤晾干,即得到含双核稀土簇合物的晶态材料。
3.根据权利要求2所述的方法,其特征在于:所述的溶解LnmXn的溶剂为水或/和有机溶剂。
4.根据权利要求3所述的方法,其特征在于:所述的有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、甲醇、乙醇、乙腈、丙酮、乙酰丙酮、二氯甲烷和三氯甲烷中的至少一种。
5.根据权利要求2所述的方法,其特征在于:所述的X为硝酸根、卤素离子、磺酸根、草酸根、醋酸根和三氟甲磺酸根中的一种。
6.根据权利要求2所述的方法,其特征在于:所述步骤(d)中混合溶液加热的环境包括大气、氮气或氧气环境,然后通过过滤去除晶体表面的溶剂。
7.根据权利要求1所述的含双核稀土簇合物的晶态材料的用途,其特征在于:所述的含双核稀土簇合物的晶态材料用于检测亚铁离子或乙醚溶剂分子。
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