CN110627819B - 以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法和应用 - Google Patents
以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种以苯并咪唑衍生物和1,2‑环己二胺构筑的镝配合物及其制备方法和应用。所述镝配合物的化学式为：[Dy(L1)(NO3)2(SCN)]，该镝配合物属于单斜晶系，P21/n空间群。所述镝配合物的制备方法为：将N‑甲基‑苯并咪唑‑2‑醛、六水合硝酸镝、硫氰酸盐和1,2‑环己二胺置于混合溶剂中，溶解后于加热或不加热条件下反应，反应物静置，有晶体析出，收集晶体，即得；其中，所述的混合溶剂为乙腈与甲醇或乙醇的组合物。本发明所述镝配合物为平面结构，对有机溶剂具有良好的发光响应，可用于检测或识别不同的有机溶剂，因此可用作敏化剂。
Description
技术领域
本发明涉及以苯并咪唑衍生物和1,2-环己二胺构筑的稀土配合物，具体涉及以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法和应用。
背景技术
配位化学在金属离子光致发光探针的设计中起着至关重要的作用。金属与有机染料的配位引起了不同的光学反应，这表明了所关注的金属种类的存在。d6、d8和d10构型的发光镧系元素和过渡金属配合物往往表现出与有机染料不同的独特发光特性，如量子产率高、燃烧量大、发射波长和发射寿命长、对微环境的敏感度低，并可作为金属离子、阴离子和中性物质的探针。
由于挥发性有机物质(VOCs)在医学、环境科学、毒理学、生物化学等方面的应用，近年来挥发性有机化合物的分析受到广泛关注。它们有助于评价工业材料的性质和质量，检测各种疾病，跟踪空气污染物。
十多年来，人们对镧系配合物的兴趣越来越大，特别是因为它们具有特殊的发光特性。考虑到4fn电子构型的众多电子能级，Ln(III)离子的特异性发射大多在可见光到红外的光谱范围内。有机发光配体通过“天线效应”，不仅作为复杂骨架的新构建体，而且作为Ln3+离子的高效敏化剂。虽然镧系化合物具有很好的发光性能和调控性能，但其对挥发性有机溶剂的发光响应目前仅限于具有三维网络结构的镧系金属有机骨架(Ln-MOFs)。Ln-MOFs的主要响应原理是有机物进入到Ln-MOFs的孔隙中导致有效的MLCT产生，使其发光性能发生变化。然而，低维镧系化合物对特定的有机物质，特别是零维镧系配位分子簇很少有良好的发光响应。因此，拓展低维镧系化合物在VOCs特异性识别中的应用是一项关键而又具有挑战性的工作。但目前尚未见有平面结构的以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其具有良好发光响应的相关报道。
发明内容
本发明要解决的技术问题是提供一种平面型氮杂多环且对有机物质具有良好发光响应的以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法和应用。
本发明所述的以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物，其化学式为：[Dy(L1)(NO3)2(SCN)]，其中，L1表示(N1E,N2E)-N1,N2-双((1-甲基-1H-苯并[d]咪唑-2-基)亚甲基)环己二胺-1,2-二胺；该镝配合物属于单斜晶系，P21/n空间群，晶胞参数为：a＝12.249
α＝90.00°，β＝90.684(9)°，γ＝90.00°。
本发明还提供上述权利要求1所述以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物的制备方法，具体为：将N-甲基-苯并咪唑-2-醛、六水合硝酸镝、硫氰酸盐和1,2-环己二胺置于混合溶剂中，溶解后于加热或不加热条件下反应，反应物静置，有晶体析出，收集晶体，即得；其中，所述的混合溶剂为乙腈与甲醇或乙醇的组合物。
上述制备方法中，N-甲基-苯并咪唑-2-醛、六水合硝酸镝、硫氰酸盐和1,2-环己二胺的摩尔比为化学计量比，在实际操作过程中，六水合硝酸镝的量可相对过量一些。所述的硫氰酸盐优选为硫氰酸钠和/或硫氰酸钾。在混合溶剂的组成中，乙腈与甲醇或乙醇的体积比为1：1-4，更优选为1：1-2。所述混合溶剂的用量可根据需要确定，通常以能溶解参加反应的原料为宜。具体地，以1mmol的N-甲基-苯并咪唑-2-醛为基准计算，全部原料所用混合溶剂的总用量通常为6-15mL。在具体溶解的步骤中，可将各原料分别用混合溶剂中的某一种组分溶解，然后再混合在一起反应；也可将所有原料混合在一起后再加混合溶剂溶解。
上述制备方法中，反应优选是在加热条件下进行，进一步优选是在≥50℃的条件下进行，更优选在60-100℃的条件下进行。当反应在60-100℃条件下进行时，反应时间通常控制在24-60h。
本申请人在实验中发现，上述以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物在不同的有机溶剂中的发光强度不同，可以用于检测或识别不同的有机溶剂。因此，本发明还包括上述以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物在制备敏化剂中的应用。
与现有技术相比，本发明提供了一类平面型氮杂多环的以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法，申请人在实验中发现，本发明所述的镝配合物对有机溶剂具有良好的发光响应，可以用于检测或识别不同的有机溶剂，因此，可用作敏化剂。
附图说明
图1为本发明实施例1制得的最终产物的晶体结构图；
图2为本发明实施例1制得的最终产物的热重分析曲线图；
图3为本发明实施例1制得的最终产物的粉末衍射曲线图；
图4为本发明实施例1制得的最终产物的甲醇溶液的紫外可见吸收曲线和发光发射曲线；
图5为本发明实施例1制得的最终产物的能量转移过程图和CIE色彩图(即色标图)，其中(a)为包括实施例1制得的最终产物在内的能量转移过程图，(b)为包括实施例1制得的最终产物在内的CIE色彩图；
图6为本发明实施例1制得的最终产物在不同有机分子(3mg/10ml)中的发射光谱曲线(313nm激发)发光强度图；其中(a)为实施例1制得的最终产物在不同有机分子(3mg/10ml)中的发射光谱曲线(307nm激发)，(b)为实施例1制得的最终产物在不同有机分子溶剂中的发光强度柱形图。
具体实施方式
下面结合具体实施例对本发明作进一步的详述，以更好地理解本发明的内容，但本发明并不限于以下实施例。
实施例1：镝配合物[Dy(L1)(NO3)2(SCN)](在本申请中也简称Dy1-SCN或配合物Dy1-SCN)的制备
将0.5mmol的N-甲基-苯并咪唑-2-醛(a,0.082g，在本申请中也简称为配体L)加入到25mL容量的聚四氟乙烯的反应釜中，10mL由乙腈和甲醇组成的混合溶剂(V乙腈：V甲醇＝1：1)，完全溶解后继续加入0.5mmol的六水合硝酸镝(0.228g)，溶解后再加入0.25mmol的硫氰酸钠(0.021g)，最后至完全溶解后，在搅拌的条件下加入0.5mmol的1,2-环己二胺(b,61μL)，继续搅拌3分钟，密封之后放入80℃的烘箱保温反应48h，取出，缓慢降温(大概12h降至室温)，有白色长条状晶体析出，收集晶体，干燥。产率57.6％(基于六水合硝酸镝)。
选取本实施例所得的尺寸适中的晶体置于安捷伦公司SuperNova单晶衍射仪上，采用石墨单色化的Mo-Kα 
射线进行单晶测试。在295K条件下，以
扫描方式在2.9°≤θ≤25.0°范围内收集到衍射点。本实施例所得产物的初始晶体结构均采用SHELXS-97和Olex-2直接法解出，几何加氢，非氢原子坐标及各向异性热参数采用SHELXL-97均经全矩阵最小二乘法精修。所得晶体学和结构精修数据如下述表1所示，部分键长键角数据如下述表2所示，所得白色长条状晶体的晶体结构如图1所示，确定所得的白色长条状晶体为配合物Dy1-SCN(即镝配合物[Dy(L1)(NO3)2(SCN)]，其中，L1表示(N1E,N2E)-N1,N2-双((1-甲基-1H-苯并[d]咪唑-2-基)亚甲基)环己二胺-1,2-二胺)。
表1：配合物Dy1-SCN的晶体结构数据表
表2：配合物Dy1-SCN的部分键长键角数据
如图1所示，配合物Dy1-SCN的空间群是P21/n，不对称单元由一个Dy，一个L3，两个硝酸根和一个硫氰酸根组成。金属中心(Dy)与螯合配体L3提供的四个N原子，两个硝酸根提供的四个O原子和硫氰酸根提供的一个N原子发生配位，Dy-N
、Dy-O
和N-Dy-O(76.5-154.5°)。平面型有机配体位于与硝酸根相反的方向。
图2为配合物Dy1-SCN的热重分析图，实验温度控制为室温到1000℃，流速为15cm3/min，升温速率为5℃/min，氮气条件下的热重分析表明，配合物Dy1-SCN没有溶剂分子，并且在接近280℃时才开始分解，说明其热稳定性好。
图3为配合物Dy1-SCN的粉末衍射图。通过粉末衍射的实验值和拟合值对比可以看出，通过上述方法合成的配合物Dy1-SCN为纯相。
对比例1-1
重复实施例1，不同的是，将混合溶剂改为甲醇、乙腈、二氯甲烷、氯仿、DMF或DMSO等单一的溶剂。结果没有晶体或其它形状(如粉末)产物生成。
对比例1-2
重复实施例1，不同的是，将混合溶剂中的乙腈用二氯甲烷、DMF或DMSO替代。结果没有晶体或其它形状(如粉末)产物生成。
对比例1-3
重复实施例1，不同的是，不同的是，用四水合醋酸镝、六水合高氯酸镝或六水氯化镝代替六水合硝酸镝，希望CH3COO-、ClO4 -或Cl-离子能取代参与配位的NO3 -离子，亦或是通过醋酸根或高氯酸根桥连得到新的结构的配合物，但均未得到晶体，说明用其它镝盐无法达到形成镝配合物和结晶的热力学条件。
实施例2：配合物1的合成
重复实施例1，不同的是，用硫氰酸钾替换硫氰酸钠，将乙腈和甲醇的体积比改为1：4。
结果得到白色长条状晶体晶体。产率50.9％(基于六水合硝酸镝)。
对本实施例所得产物经单晶衍射分析，确定所得白色长条状晶体为配合物Dy1-SCN。
实施例3：配合物1的合成
重复实施例1，不同的是，将反应改在100℃条件下进行，反应的时间为24h；将混合溶剂改为乙腈和乙醇的组合物，其中乙腈和乙醇的体积比改为1：1。
结果得到白色长条状晶体晶体。产率57.6％(基于六水合硝酸镝)。
对本实施例所得产物经单晶衍射分析，确定所得白色长条状晶体为配合物Dy1-SCN。
实施例4：配合物1的合成
重复实施例1，不同的是，用硫氰酸钾替换硫氰酸钠，将反应改在50℃条件下进行，反应的时间为60h；将混合溶剂改为乙腈和乙醇的组合物，其中乙腈和乙醇的体积比改为1：2。
结果得到白色长条状晶体晶体。产率55.7％(基于六水合硝酸镝)。
对本实施例所得产物经单晶衍射分析，确定所得白色长条状晶体为配合物Dy1-SCN。
实施例5：配合物Dy1-SCN应用于检测不同有机溶剂
取一定量的配合物Dy1-SCN晶体和配体L1分别溶解于甲醇(在本申请中，如果没有特别说明，所述的甲醇均是指无水甲醇)中，配制成浓度为1*10-4mol/L的溶液，并进行紫外-可见吸收测定，配合物Dy1-SCN甲醇溶液的紫外可见荧光激发光谱分别如图4中左边曲线所示。由图可知，配合物Dy1-SCN在甲醇溶液中的紫外吸收峰分别是230nm和310nm(而配体L1在364nm有很强的吸收峰)。配合物通常呈现出光谱属性一般是由于特殊的镧系金属离子的电子层结构而引起的。因此，本申请人在室温下测试了溶解在甲醇溶液中的Dy1-SCN的发光性能，室温下得到了配合物Dy1-SCN在溶液状态下的发光特性，四种溶液的紫外可见荧光发射光谱分别如图4中右边曲线所示。结果发现，本发明所述配合物在甲醇中的发光强度与在紫外灯下观察到的不一致，本申请人推测甲醇溶剂可能对配合物的发光起猝灭作用。
上述单核配合物Dy1-SCN溶于甲醇，主要表现为有机配体和镧系金属离子的发光行为。为了更好地理解上述单核配合物的发光行为，本申请人提出采用一个如图5(a)所示的简单的模型来解释其发光特性，能量转移模型表明，Ln(III)离子(DyIII、TbIII、EuIII)可以接受有机配体L1的电子和能量转移进行荧光发射，通过CIE颜色坐标可以看出，Ln(Ln＝Dy,Tb,Eu)在甲醇溶液中主要发出蓝绿色和红光，如图5(b)所示，CIE彩色图中配合物Dy1-SCN的颜色坐标为Dy1-SCN(0.226,0.182)。
因本申请人发现配合物在甲醇中的发光强度与在紫外灯下观察到的不一致，因而推测甲醇溶剂可能对配合物的发光起猝灭作用。因此，本申请还特别研究了配合物Dy1-SCN在不同溶剂(MeOH,CH2Cl2,CHCl3,DMF,1,4-dioxane,H2O,THF,EtOAc,acetone,EtOH,n-heptane,DMSO,benzene,CH3CN,CCI4,PET(petroleum ether),and toluene)中的发光，如图6(a)Dy1-SCN在不同有机分子(3mg/10ml)中的发射光谱(307nm激发)；(b)Dy1-SCN在不同有机分子溶剂中的发光强度。
当采用307nm的激发波长在不同的有机溶剂中激发Dy1-SCN时，发现溶解在二氯甲烷(CH2Cl2)中的Dy1-SCN的发射峰明显高于其他有机溶剂。当Dy1-SCN在PET中溶解分散时，主要在433nm处表现出较强的发射宽峰，在749nm处表现出较强的发射峰。这个433nm的发射峰可以被归为配体L的π-π*的能级跃迁，而在749nm处的发射峰可以被归为Dy(III)离子的4F2/9→6H13/2的能级跃迁。
Claims (7)
1.以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物，其特征在于：
该镝配合物的化学式为：[Dy(L1)(NO3)2(SCN)]，其中，L1表示(N1E,N2E)-N1,N2-双((1-甲基-1H-苯并[d]咪唑-2-基)亚甲基)环己二胺-1,2-二胺；
该镝配合物属于单斜晶系，P21/n空间群，晶胞参数为：
α＝90.00°，β＝90.684(9)°，γ＝90.00°。
2.权利要求1所述以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物的制备方法，其特征在于：将N-甲基-苯并咪唑-2-醛、六水合硝酸镝、硫氰酸盐和1,2-环己二胺置于混合溶剂中，溶解后于加热或不加热条件下反应，反应物静置，有晶体析出，收集晶体，即得；其中，所述的混合溶剂为乙腈与甲醇或乙醇的组合物。
3.根据权利要求2所述的制备方法，其特征在于：所述混合溶剂的组成中，乙腈与甲醇或乙醇的体积比为1：1-4。
4.根据权利要求2所述的制备方法，其特征在于：所述的硫氰酸盐为硫氰酸钠和/或硫氰酸钾。
5.根据权利要求2所述的制备方法，其特征在于：反应在≥50℃的条件下进行。
6.根据权利要求2所述的制备方法，其特征在于：反应在60-100℃的条件下进行。
7.权利要求1所述的以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物在制备二氯甲烷的敏化剂中的应用。
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