CN111909183B - 一种叔丁基吡啶吡唑铜[i]双核配合物刺激响应发光变色材料的制备方法 - Google Patents
一种叔丁基吡啶吡唑铜[i]双核配合物刺激响应发光变色材料的制备方法 Download PDFInfo
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- LIYFCHNXHNTGPK-UHFFFAOYSA-N FC(C1=CC(C2=CC=CN=C2C2=NC=CC=C2)=NN1)(F)F Chemical compound FC(C1=CC(C2=CC=CN=C2C2=NC=CC=C2)=NN1)(F)F LIYFCHNXHNTGPK-UHFFFAOYSA-N 0.000 description 1
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- NMIPCXQNFDQXHZ-UHFFFAOYSA-N [Cu].N1N=CC=C1.FC(F)(F)C1=NC=CC=C1 Chemical compound [Cu].N1N=CC=C1.FC(F)(F)C1=NC=CC=C1 NMIPCXQNFDQXHZ-UHFFFAOYSA-N 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法，包括以下步骤：S1，在氩气气氛下，将混合原料在二氯甲烷溶剂或乙腈‑二氯甲烷混合溶剂中进行常温搅拌反应；S2，将步骤S1中无色透明溶液用旋转蒸发仪减压蒸干；S3，将步骤S2中蒸干后得到的固体物用二氯甲烷‑正己烷混合溶剂进行重结晶，并过滤得到的无色晶态产物；S4，将步骤S3中的无色晶态产物用乙醚进行洗涤；S5，将步骤S4中洗涤后的无色晶态产物真空干燥，得到无色固体产物，使用本发明的制备方法得到的铜[I]配合物发光材料对于机械研磨和二氯甲烷蒸汽均具有刺激响应特性，可用于制作能感应和检测机械研磨作用和二氯甲烷蒸汽的智能发光传感器的元件。
Description
技术领域
本说明书一个或多个实施例涉及刺激响应发光变色新材料合成领域，尤其涉及一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法。
背景技术
受强自旋轨道耦合作用和重原子效应影响，金属发光配合物理论上可利用所有单重态和三重态能量，大幅改善发光效率。当前，金属发光配合物主要应用第五、六周期的过渡金属，尤其是第VIII族的过渡金属，如钌、锇、铱、铂。然而，第五、六周期的过渡金属(除第一、二副族的少数几种金属外)在地壳中含量稀少且开采困难，因此，该类贵金属基发光材料的使用成本较高，而且大规模应用后还会带来原材料紧缺问题。此外，该类贵金属化合物通常有较大毒性，尤其是钌、锇、铼等金属化合物。因而，该类贵金属化合物发光材料在大规模应用后不仅会带来环境污染还会给生产和使用者带来直接或间接伤害。高使用成本及对环境不友好等缺陷使得它们的大规模应用受到诸多限制，因此特别期望能够在第五、六周期之外找寻到其它可替代的金属元素。
相较第五、六周期的过渡金属，第四周期的金属铜，不仅资源丰富，价格低廉，而且发光优良，环境友好。此外，一价铜配合物具有良好的室温可见磷光发射，其发光可在紫外至近红外区变化，涵盖整个可见光区。资源丰富、价格低廉、发光优良、环境友好等诸多优点使得一价铜发光配合物在发光器件、智能材料、光学传感等众多领域具有良好的应用前景。
目前，公开报道的一价铜发光配合物主要是一价铜单核配合物和多核簇合物。一价铜簇合物因其结构新颖，构型丰富，配位多样，发光优良等优点，越来越受到人们的重视。然而，应用氮唑基多齿配体和有机双膦配体的组合，构建一价铜配合物发光变色材料的文献报道却很少，尤其是一价铜配合物刺激响应发光变色材料，综上所述，本申请现提出一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法来解决上述出现的问题。
发明内容
有鉴于此，本说明书一个或多个实施例的目的在于提出一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法，以解决背景技术中提出的问题。
基于上述目的，本说明书一个或多个实施例提供了一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法，包括以下步骤：
S1，在氩气气氛下，将适量的混合原料在二氯甲烷溶剂或乙腈-二氯甲烷混合溶剂中进行常温搅拌反应，得到无色透明溶液；
S2，将步骤S1中的无色透明溶液用旋转蒸发仪减压蒸干；
S3，将步骤S2中蒸干后得到的固体物用二氯甲烷-正己烷混合溶剂进行重结晶，过滤经重结晶得到的无色晶态产物；
S4，将步骤S3中的无色晶态产物用乙醚进行洗涤；
S5，将步骤S4中洗涤后的无色晶态产物真空干燥，得到无色固体产物。
优选的，所述混合原料为摩尔比为1:1:1的[Cu[CH3CN]4][ClO4]、双二苯基膦甲烷和5-叔丁基-3-[2-吡啶基]吡唑。
优选的，所述混合原料为摩尔比为1:5-10:2:2的[Cu[ClO4]2·6H2O]、过量铜粉、双二苯基膦甲烷和5-叔丁基-3-[2-吡啶基]吡唑，并将混合原料投入乙腈-二氯甲烷混合溶剂中进行常温搅拌反应。
更为优选的，所述步骤S1中的乙腈-二氯甲烷混合溶剂的两种溶剂的体积比为1:2。
优选的，所述步骤S1中的常温搅拌反应的时间为2-4h。
优选的，所述步骤S3中二氯甲烷-正己烷混合溶剂的两种溶剂的体积比为1:10。
优选的，所述步骤S4中无色晶态产物利用乙醚洗涤3-4次。
叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料，分子式为C74H74Cl2Cu2N6O8P4。
从上面所述可以看出，本发明的有益效果：本发明提供一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料以及叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法。
本发明的叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料选用 5-叔丁基-3-[2-吡啶基]吡唑和双二苯基膦甲烷的主要目的和意义：选用具有螯合功能的多齿配体5-叔丁基-3-[2-吡啶基]吡唑和具有桥联功能的二齿双膦配体双二苯基膦甲烷，主要用于调控铜[I]配合物的空间立体效应、电子密度分布和N-H电子特性，实现铜[I]配合物完全可逆的刺激响应发光变色性能。在常温下，该铜[I]配合物固体颗粒的发光波长最大值为464nm，发光寿命为42μs，发光量子效率为21％。当该固体颗粒被研磨后，其固体粉末的发光波长最大值变为512nm，发光寿命为20μs，发光量子效率为7％，而当该研磨后的固体粉末放置于二氯甲烷蒸汽气氛中后，其发光波长最大值变为465nm，发光寿命为39μs，发光量子效率为17％；当该固体粉末再次被研磨后，其发光波长最大值重新变为512nm，而当该研磨后的固体粉末再次放置于二氯甲烷蒸汽气氛中后，其发光波长最大值也重新变为 465nm；周而复始，不断循环。研究结果表明本发明的三氟甲基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料，在机械研磨作用下会产生发光变色性质，而在二氯甲烷蒸汽下又能恢复原来的发光，即本发明的铜[I]配合物发光材料对于机械研磨和二氯甲烷蒸汽均具有刺激响应特性，可用于制作能感应和检测机械研磨作用和二氯甲烷蒸汽的智能发光传感器的元件。
附图说明
为了更清楚地说明本说明书一个或多个实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本说明书一个或多个实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明中叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的分子结构图；
图2为本发明中叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法的一种优选的反应机理图；
图3为本发明中叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法的另一种优选的反应机理图；
图4为本发明中叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的晶体结构图；
图5为本发明中叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的固态荧光发射光谱图。
具体实施方式
为使本公开的目的、技术方案和优点更加清楚明白，以下结合具体实施例，对本公开进一步详细说明。
需要说明的是，除非另外定义，本说明书一个或多个实施例使用的技术术语或者科学术语应当为本公开所属领域内具有一般技能的人士所理解的通常意义。本说明书一个或多个实施例中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
实施例一
如图2所示，一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的制备方法，包括以下步骤：
S1，在氩气气氛下，将适量的混合原料在二氯甲烷溶剂中进行常温搅拌反应，得到无色透明溶液；
S2，将步骤S1中的无色透明溶液用旋转蒸发仪减压蒸干；
S3，将步骤S2中蒸干后得到的固体物用二氯甲烷-正己烷混合溶剂进行重结晶，过滤经重结晶得到无色晶态产物；
S4，将步骤S3中的无色晶态产物用乙醚进行洗涤；
S5，将步骤S4中洗涤后的无色晶态产物真空干燥，得到无色固体产物。
作为上述方案的改进方案，所述混合原料为摩尔比为1:1:1的 [Cu[CH3CN]4][ClO4]、双二苯基膦甲烷和5-叔丁基-3-[2-吡啶基]吡唑。
作为上述方案的改进方案，所述步骤S1中的常温搅拌反应的时间为 2-4h。
作为上述方案的改进方案，所述步骤S3中二氯甲烷-正己烷混合溶剂的两种溶剂的体积比为1:10。
作为上述方案的改进方案，所述步骤S4中无色晶态产物利用乙醚洗涤 3-4次。
如图1所示，叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料，分子式为C74H74Cl2Cu2N6O8P4，中文名称为高氯酸根·二[5-叔丁基-3-[2-吡啶基]吡唑]·二[双二苯基膦甲烷]合二铜[I]配合物，英文名称为 [Cu2[5-tert-butyl-3-(2-pyridyl)pyrazole]2[bis(diphenylphosphino)methane]2][ClO 4]2，分子量为1497.31。
在氩气气氛下，[Cu[CH3CN]4][ClO4](24.2mg，0.074mmol)、双二苯基膦甲烷(28.5mg，0.074mmol)和5-叔丁基-3-[2-吡啶基]吡唑(14.9mg， 0.074mmol)在10mL二氯甲烷中常温搅拌反应2小时，得到无色透明溶液，后用旋转蒸发仪将溶剂减压蒸干，用二氯甲烷-正己烷混合溶剂[体积比为 1:10]进行重结晶，过滤重结晶得到的无色晶态产物，用乙醚洗涤4次，真空干燥后得到无色固体产物(43.5mg，0.029mmol)，经检测得到产率为78％。
元素分析计算值(C74H74Cl2Cu2N6O8P4)为(％)：C59.36,H4.98,N5.61；实测值：C59.41，H4.95，N5.58。
X-射线单晶衍射：晶体属单斜晶系，P 21/c空间群，晶胞参数：a＝ 13.5675(9)，b＝17.0941(11)，
β＝91.593(2)°，
Z＝2，formula＝C74H74Cl2Cu2N6O8P4·C6H14，Mr＝1583.42，Dc＝1.359g cm-3，μ＝0.760mm-1，GOF＝1.048，晶体结构图如图4所示。
光致发光性能测试结果表明，该铜[I]双核配合物固体在常温下表现可逆的刺激响应发光变色性能。在常温下，该铜[I]配合物固体颗粒的发光波长最大值为464nm，发光寿命为42μs，发光量子效率为21％。当该固体颗粒被研磨后，其固体粉末的发光波长最大值变为512nm，发光寿命为20μs，发光量子效率为7％，而当该研磨后的固体粉末放置于二氯甲烷蒸汽气氛中后，其发光波长最大值变为465nm，发光寿命为39μs，发光量子效率为17％；当该固体粉末再次被研磨后，其发光波长最大值重新变为512nm，而当该研磨后的固体粉末再次放置于二氯甲烷蒸汽气氛中后，其发光波长最大值也重新变为465nm；周而复始，不断循环。其固态荧光发射光谱图如图5所示。
实施例二
如图3所示，作为另一种优选方案，所述混合原料为摩尔比为1:5-10:2:2 的[Cu[ClO4]2·6H2O]、过量铜粉、双二苯基膦甲烷和5-叔丁基-3-[2-吡啶基] 吡唑，并将混合原料投入乙腈-二氯甲烷混合溶剂进行常温搅拌反应。
作为上述方案的改进方案，所述步骤S1中的乙腈-二氯甲烷混合溶剂的两种溶剂的体积比为1:2。
在氩气气氛下，六水高氯酸铜[Cu[ClO4]2·6H2O](16.7mg，0.045mmol) 和过量铜粉(19.0mg，0.299mmol)在5mL乙腈中常温搅拌反应30分钟，后加入双二苯基膦甲烷(34.6mg，0.090mmol)的10mL二氯甲烷溶液，继续搅拌反应1小时后加入5-三氟甲基-3-[2-吡啶基]吡唑配体(18.1mg， 0.090mmol)，常温下继续搅拌反应2小时，过滤后用旋转蒸发仪将溶剂减压蒸干，用二氯甲烷(2mL)-正己烷(20mL)混合溶剂进行重结晶，过滤重结晶得到的无色晶态产物，用12mL乙醚洗涤4次，真空干燥得到无色固体产物(49.9mg，0.033mmol)，经检测得到产率为73％。
元素分析计算值(C74H74Cl2Cu2N6O8P4)为(％)：C59.36,H4.98,N5.61；实测值：C59.41，H4.95，N5.58。
X-射线单晶衍射：晶体属单斜晶系，P 21/c空间群，晶胞参数：a＝ 13.5675(9)，b＝17.0941(11)，
β＝91.593(2)°，
Z＝2，formula＝C74H74Cl2Cu2N6O8P4·C6H14，Mr＝1583.42，Dc＝1.359g cm-3，μ＝0.760mm-1，GOF＝1.048，晶体结构图如图4所示。
光致发光性能测试结果表明，该铜[I]双核配合物固体在常温下表现可逆的刺激响应发光变色性能。在常温下，该铜[I]配合物固体颗粒的发光波长最大值为464nm，发光寿命为42μs，发光量子效率为21％。当该固体颗粒被研磨后，其固体粉末的发光波长最大值变为512nm，发光寿命为20μs，发光量子效率为7％，而当该研磨后的固体粉末放置于二氯甲烷蒸汽气氛中后，其发光波长最大值变为465nm，发光寿命为39μs，发光量子效率为17％；当该固体粉末再次被研磨后，其发光波长最大值重新变为512nm，而当该研磨后的固体粉末再次放置于二氯甲烷蒸汽气氛中后，其发光波长最大值也重新变为465nm；周而复始，不断循环。其固态荧光发射光谱图如图5所示。
本说明书一个或多个实施例旨在涵盖落入所附权利要求的宽泛范围之内的所有这样的替换、修改和变型。因此，凡在本说明书一个或多个实施例的精神和原则之内，所做的任何省略、修改、等同替换、改进等，均应包含在本公开的保护范围之内。
Claims (1)
1.一种叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料的应用，其特征在于，包括：所述叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料为高氯酸根·二[5-叔丁基-3-[2-吡啶基]吡唑]·二[双二苯基膦甲烷]合二铜[I]配合物，其分子式为C74H74Cl2Cu2N6O8P4，分子量为1497.31，其分子结构为：
其中，所述叔丁基吡啶吡唑铜[I]双核配合物刺激响应发光变色材料在机械研磨作用下会产生发光变色性质，而在二氯甲烷蒸汽下又能恢复原来的发光。
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