CN105440064B - 稀土配合物及其制备方法 - Google Patents
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Abstract
本发明涉及利用挥发法制备荧光量子产率大于60%的稀土配合物及其制备方法。包括如下制备步骤:a)将LnmXn溶解于溶液中备用;b)将脱质子的3‑氯‑2,4‑二氟苯甲酸溶液,加入a)溶液中;c)将以上混合溶液放置挥发者加热挥发,一段时间后能看到有粉末或者晶体析出,d)将上一步得到的粉末或者晶体过滤晾干。该方法简单易行,设计合理,适用于各类金属离子和配体,且制备稀土配合物晶体的方法简便,无需贵重的仪器设备,具有很强的创造性。
Description
技术领域
本发明涉及高荧光量子产率稀土配位化合物制备技术领域,具体涉及利用挥发法制备荧光量子产率大于60%的稀土配合物的制备方法。
背景技术
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)。稀土元素外层电子结构相同,内层的4f电子能级相近,使含稀土元素的配合物表现出许多独特的物理和化学性质,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;配合物是金属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,配合物的设计与合成是配位化学研究的重要内容。为提高稀土离子的发光强度,人们常采用含有共轭基团的有机配体与Ln3+离子配位形成稀土配合物,此类配体的吸光系数大,并能将吸收的能量有效地传递给Ln3+,从而敏化稀土离子,显著提高Ln3+离子的发光强度。
稀土配合物具有独特的荧光性质,如:长毫秒级的荧光寿命、窄带发射、较大的Stokes位移、发光区域遍及可见光区如:Sm3+、Eu3+、Tb3+、Dy3+的发射和近红外区如:Nd3+、Er3 +、Yb3+的发射。配体中的官能团,以及与稀土离子配位的分子/离子中含有的O-H,N-H和C-H会影响稀土配合物中稀土离子发光的某些过程或阶段,例如:影响能量从配体向稀土离子的传递、影响配合物中稀土离子的环境、影响配位基团的振动、影响配体的光吸收等,从而改变稀土离子的荧光量子产率、荧光寿命等性质。利用这些荧光性质的变化,就能设计合成出高荧光量子产率的稀土配合物。
稀土离子的外层电子处于f轨道,直接激发时发光效率很低,所以需要具有共轭基团的配体与稀土离子配位当作“天线”,才能有效地吸收光子的能量而产生有效的荧光发射。基于此,科学家们在合成高荧光量子产率稀土配合物方面做了一些探索和有意义的工作。如Parker教授2014年在Angew.Chem.Int.Edit.上报道了一例在水中荧光量子产率达到28%的稀土配合物;Mazzanti教授采用乙酰丙酮衍生物合成的稀土配合物荧光量子产率高达70%;Ogo教授采用三氮杂环类配体合成的稀土配合物在稀硫酸溶液中荧光量子产率高达50%,而在氮气氛围中荧光量子产率提高到90%;Pecoraro教授2014年在JACS报道的稀土配合物近红外荧光量子产率可达到3.8%;严纯华教授2014年发表在Nat.Commun.的稀土化合物荧光上转换效率高达16%。申请人在2014年也报道了一例通过调节配位溶剂分子,使铽(III)配合物荧光量子产率从4%突变到46%,但是,与有机发光材料接近100%的荧光量子产率相比,稀土配合物的荧光量子产率还是偏低,这正是稀土配合物发光领域亟待解决的难题。
发明内容
本发明所要解决的技术问题是提供具有高荧光量子产率的稀土配合物及其制备方法。
为解决上述技术问题,本发明提供以下技术方案:
本发明中的稀土配合物是由稀土元素,配体3-氯-2,4-二氟苯甲酸和2,2’联吡啶构筑的配合物,所述稀土元素包括:Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的至少一种。
本发明中稀土配合物的制备方法包括如下步骤:a)将LnmXn溶解于溶液中备用,上试中Ln为稀土离子,X为阴离子,m和n为自然数;
b)将脱质子的3-氯-2,4-二氟苯甲酸溶液,以及2,2’联吡啶溶液加入步骤a)中的溶液中;
c)将以上混合溶液放置挥发或者加热挥发,一段时间后能看到有粉末或者单晶析出;
d)将上一步得到的粉末或者单晶过滤晾干。
本发明中的稀土配合物也可以通过另外一种途径制备,具体制备途径如下:1)将3-氯-2,4-二氟苯甲酸溶液脱质子,加入2,2’联吡啶溶液混合均匀;
2)将LnmXn溶解于溶液中,上述试中Lnm=稀土离子,X=阴离子,m和n为自然数;
3)将由步骤1)得到的溶液和步骤2)制得的溶液混合均匀,混合溶液放置挥发或者加热挥发,一段时间后能看到有粉末或者单晶析出;
4)将上一步得到的粉末或者晶体过滤,晾干,即得到了荧光量子产率高于60%的Tb配合物。
所述步骤c)和步骤3)中混合溶液的挥发环境包括在大气中以及在其他气体环境中,并且通过挥发去除溶剂得到稀土配合物。
溶解LnmXn,2,2’联吡啶和3-氯-2,4-二氟苯甲酸的溶剂为水或/和有机溶剂。
优选的,所述有机溶剂为二甲基亚砜、N,N-二甲基甲酰胺、四氢呋喃、甲醇、乙醇、丙酮、乙腈,二氯甲烷和三氯甲烷中的至少一种。
本发明与现有技术相比具有的有益效果是:其中,本发明以3-氯-2,4-二氟苯甲酸,2,2’联吡啶和稀土金属盐为原料,应用挥发法制备了具有高荧光量子产率的稀土配合物单晶,其绝对荧光量子产率高于60%;其中,本发明中稀土配合物晶体的制备不同于以往的物理或化学方法,它是通过采用含O-H,N-H和C-H振荡器较少的配体,以及可以挤掉水分子配位的辅助配体2,2’联吡啶与稀土盐放置反应,通过挥发法长出晶体,该方法简单易行,设计新颖合理,适用于各类金属离子和配体,且制备稀土配合物单晶的方法简便,无需贵重的仪器设备。
附图说明
图1以稀土Tb合成的稀土配合物的结构示意图;
图2与Tb配位的原子以扭曲的二帽三棱柱的方式排列图;
图3配体与Tb的配位模式图;
图4合成的Tb配合物的荧光衰减图;
图5合成的Tb配合物的激光和发射光谱图。
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。
实施例1,Tb配合物的制备及其晶体结构。
(1)将11.0mg 3-氯-2,4-二氟苯甲酸置于烧杯中,加入1ml水,并用氢氧化钠溶液调节pH为6,得溶液A;
(2)将8.7mg Tb(NO3)3·6H2O与2.9mg 2,2’联吡啶混合,加入2ml乙酰丙酮溶解,得溶液B;
(3)将溶液A和溶液B混合,所得混合液于室温内挥发,得到无色晶体新稀土化合物I。
单晶结构分析表明新稀土化合物I为三斜晶系,新稀土化合物I的P-1空间群11.1669(8),b=11.2383(8), Z=1,其分子式为Tb2C62H32Cl8F14N4O14,新稀土化合物I是双核的分子,相邻的双核结构通过氢键连接起来,构筑成三维的超分子网络结构。从图4中可以看出新稀土化合物I的激发波长为318nm,在489nm、545nm、585nm、621nm处有明显的荧光发射峰,从图4中可以看出稀土化合物I的荧光寿命为1.0ms。
实施例2,新稀土配合物II的制备。
(1)将10.0mg 3-氯-2,4-二氟苯甲酸置于烧杯中,加入2ml水,并用氢氧化钠溶液调节pH为5,得溶液C;
(2)将7.8mg Tb(NO3)3·6H2O与2.0mg 2,2’联吡啶混合,加入2ml乙酰丙酮溶解,得溶液D;
(3)将溶液C和溶液D混合,所得混合液于室温内挥发,得到无色晶体新稀土化合物II。
通过分析新稀土化合物II的晶体结构确认其与实施例1中的新稀土化合物I为同一物质。
实施例3,新稀土配合物III的制备及其晶体结构。
(1)将12.0mg 3-氯-2,4-二氟苯甲酸置于烧杯中,加入2ml水,并用氢氧化钠溶液调节pH为5,得溶液E;
(2)将6.0mg Gd(NO3)3与3.0mg 2,2’联吡啶混合,加入3ml乙酰丙酮溶解,得溶液F;
(3)将溶液E和溶液F混合,所得混合液于室温内挥发,得到无色晶体新稀土化合物III。
单晶结构分析表明新稀土化合物III为三斜晶系,新稀土化合物III的P-1空间群11.1672(8),b=11.2201(8), Z=1,其分子式为Gd2C62H32Cl8F14N4O14,新稀土化合物III是双核的分子,相邻的双核结构通过氢键连接起来,构筑成三维的超分子网络结构。
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 (1)
1.一种Tb稀土配合物的制备方法,其特征在于,包括如下步骤:
(1)将11.0mg 3-氯-2,4-二氟苯甲酸置于烧杯中,加入1ml水,并用氢氧化钠溶液调节pH为6,得溶液A;
(2)将8.7mg Tb(NO3)3·6H2O与2.9mg 2,2’联吡啶混合,加入2ml乙酰丙酮溶解,得溶液B;
(3)将溶液A和溶液B混合,所得混合液于室温内挥发,得到无色晶体新稀土化合物I;单晶结构分析表明新稀土化合物I为三斜晶系,新稀土化合物I属于P-1空间群,a=11.1669(8),b=11.2383(8), α=72.9760(10)°,β=69.4420(10)°,γ=67.6760(10)°,Z=1,其分子式为Tb2C62H32Cl8F14N4O14,新稀土化合物I是双核的分子,相邻的双核结构通过氢键连接起来,构筑成三维的超分子网络结构。
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