CN105541878A - 一种具有发光特性的过渡金属簇合物及其制备方法 - Google Patents
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 27
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
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- 238000000034 method Methods 0.000 abstract description 4
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- 239000003446 ligand Substances 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- 238000007210 heterogeneous catalysis Methods 0.000 abstract 1
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- 239000002243 precursor Substances 0.000 abstract 1
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Abstract
一种具有发光特性的过渡金属簇合物，化学式为[Zn6L4(N3)4]，式中L为1,1-[7,7ˊ-二-(8-羟基负离子喹啉)]，该过渡金属簇合物属于单斜晶系，空间群为C2/c，晶胞参数为α＝90.0°，β＝101.89°，γ＝90.0°，该簇合物包含六个锌离子，四个叠氮离子，四个L配体。本发明的优点是：该制备方法工艺简单、易于控制，在密闭体系中可有效防止有毒物质挥发和制备对空气敏感的前驱体；制备的过渡簇配合物结构新颖、性质优良，在表面科学、均相催化剂、多相催化、发光器件和化学传感器领域具有良好的潜在应用价值。
Description
技术领域
本发明涉及具有发光特性的荧光材料，特别是一种具有发光特性的过渡金属簇合物及其制备方法。
背景技术
过渡金属簇合物，简称过渡金属簇，含有两个或两个以上具有过渡金属的原子群。过渡金属簇合物的尺寸规格和物理特性在连接微观和宏观世界、量子论和经典系统发挥着核心作用。过渡金属簇合物在低温下展现单分子磁性(SMMs)，作为宏观理论磁体，他们显示出磁性双稳态，与此同时，他们也表现出磁量子隧效应(QTM)。过渡金属簇合物中存在着一定程度的金属-金属相互作用，金属与配体的多种结合方式，中心簇骼的多变价态和电子结构、电荷的不同离域程度等特点，使得簇合物在表面科学、均相催化剂、多相催化、生物科学、材料科学领域具有潜在的应用。8-羟基喹啉是既是一种一元双齿螯合配体，又是一种良好的发色团，在材料领域得到了广泛的应用。8-羟基喹啉及其衍生物可以和许多金属离子螯合，如与Mg2+、Zn2+、Cu2+等金属离子形成配位数为4的配合物，与Al3+、Fe3+、Ga3+金属离子形成配位数为6的配合物，还可形成配位数为8的配合物。这些配合物光/电致发光和电荷转移特性可以通过改变中央金属离子和配体结构而改变。此外，较高热稳定性、卓越的电子传递特性和独特的荧光特性，使得8-羟基喹啉类金属簇合物更多的关注。
发明内容
本发明目的是针对上述技术分析，提供一个具有发光特性的过渡金属簇合物及其制备方法，该制备方法工艺简单、易于控制，在密闭体系中可以有效的防止有毒物质的挥发和制备对空气敏感的前驱体；制备的过渡簇配合物结构新颖、性质优良，具有良好的潜在应用价值。
本发明的技术方案：
一种具有发光特性的过渡金属簇合物，化学式为[Zn6L4(N3)4]，式中L为1,1-[7,7'-二-(8-羟基负离子喹啉)]，该过渡金属簇合物属于单斜晶系，空间群为C2/c，晶胞参数为α＝90.0°，β＝101.89°，γ＝90.0°，该簇合物包含六个锌离子，四个叠氮离子，四个L配体，晶体结构如下所示
一种所述具有发光特性的过渡金属簇合物的制备方法，步骤如下：
1)将8-羟基喹啉、六水硝酸锌、叠氮钠、乙醇-水混合溶剂装入聚四氟乙烯反应釜中，在24小时内升温到140℃，然后恒温3天，最后在24小时降温到室温，得到黄色条状晶体；
2)收集上述黄色条状晶体并用乙醇洗涤，真空干燥后，制得目标产品[Zn6L4(N3)4](L＝1,1-[7,7'-二-(8-羟基负离子喹啉)])。
所述乙醇-水混合溶剂中乙醇与水的体积比为1:1；8-羟基喹啉、六水硝酸锌、叠氮钠与乙醇-水混合溶剂的摩尔比为0.75:1:2。
本发明的优点是：
该制备方法工艺简单、易于控制，在密闭体系中可以有效的防止有毒物质的挥发和制备对空气敏感的前驱体；制备的过渡簇配合物结构新颖、性质优良，在表面科学、均相催化剂、多相催化、发光器件和化学传感器领域具有良好的潜在应用价值。
附图说明
图1是该过渡金属簇合物的固体紫外-可见吸收光谱。
图2是该过渡金属簇合物的固体光致发光谱图。
具体实施方式
实施例：
一种具有发光特性的过渡金属簇合物，化学式为[Zn6L4(N3)4]，式中L为1,1-[7,7'-二-(8-羟基负离子喹啉)]，该过渡金属簇合物属于单斜晶系，空间群为C2/c，晶胞参数为α＝90.0°，β＝101.89°，γ＝90.0°，该簇合物包含六个锌离子，四个叠氮离子，四个L配体，晶体结构如下所示
所述具有发光特性的过渡金属簇合物的制备方法，步骤如下：
1)将8-羟基喹啉、六水硝酸锌、叠氮钠、乙醇-水混合溶剂装入聚四氟乙烯反应釜中，在24小时内升温到140℃，然后恒温3天，最后在24小时降温到室温，得到黄色条状晶体，所述乙醇-水混合溶剂中乙醇与水的体积比为1：1；8-羟基喹啉、六水硝酸锌、叠氮钠与乙醇-水混合溶剂的摩尔比为0.75：1：2；
2)收集上述黄色条状晶体并用乙醇洗涤，真空干燥后，制得具有发光特性的过渡金属簇合物[Zn6L4(N3)4]，式中L为1,1-[7,7'-二-(8-羟基负离子喹啉)]。
使用如下仪器及方法对产物进行表征：
挑选尺寸为0.20×0.20×0.20mm3的晶体用于单晶结构分析，单晶衍射数据在BrukerSmart1000CCD衍射仪上收集，用石墨单色器单色化的Mokα射线( )，1.75°≤θ≤27.96°。所得化合物属于单斜晶系，空间群皆为C2/c，晶胞参数大约为α＝90.0°，β＝101.89°，γ＝90.0°。晶体结构使用Origin,Diamond软件绘制。
图1是过渡金属簇合物的紫外-可见吸收光谱，在室温下由日本公司日立U-3990紫外分光光度计测试。图中表明：该簇合物的最大吸收峰位置为350nm。
图2是簇合物的固体光致发光谱图，在室温条件下使用日本F-7000荧光分光光度计进行测试后绘制。图中表明：簇合物在350nm激发波长下,其固体荧光发射峰分别为509nm，具有极好的发光性能。
Claims (3)
1.一种具有发光特性的过渡金属簇合物，其特征在于：化学式为[Zn6L4(N3)4]，式中L为1,1-[7,7'-二-(8-羟基负离子喹啉)]，该过渡金属簇合物属于单斜晶系，空间群为C2/c，晶胞参数为α＝90.0°，β＝101.89°，γ＝90.0°，该簇合物包含六个锌离子，四个叠氮离子，四个L配体，晶体结构如下所示
2.一种如权利要求1所述具有发光特性的过渡金属簇合物的制备方法，其特征在于步骤如下：
1)将8-羟基喹啉、六水硝酸锌、叠氮钠、乙醇-水混合溶剂装入聚四氟乙烯反应釜中，在24小时内升温到140℃，然后恒温3天，最后在24小时降温到室温，得到黄色条状晶体；
2)收集上述黄色条状晶体并用乙醇洗涤，真空干燥后，制得目标产品[Zn6L4(N3)4](L＝1,1-[7,7'-二-(8-羟基负离子喹啉)])。
3.根据权利要求2所述具有发光特性的过渡金属簇合物的制备方法，其特征在于：所述乙醇-水混合溶剂中乙醇与水的体积比为1:1；8-羟基喹啉、六水硝酸锌、叠氮钠与乙醇-水混合溶剂的摩尔比为0.75:1:2。
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| CN113718338A (zh) * | 2021-09-07 | 2021-11-30 | 辽宁石油化工大学 | 一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用 |
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| CN102516278A (zh) * | 2011-12-19 | 2012-06-27 | 天津理工大学 | 一种原位配体生成并配位结晶的镧系配合物及制备方法 |
| CN103965225A (zh) * | 2014-04-05 | 2014-08-06 | 安庆师范学院 | 8-氨基喹啉叠氮锌金属配合物及其制备方法和应用 |
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| CN102516278A (zh) * | 2011-12-19 | 2012-06-27 | 天津理工大学 | 一种原位配体生成并配位结晶的镧系配合物及制备方法 |
| CN103965225A (zh) * | 2014-04-05 | 2014-08-06 | 安庆师范学院 | 8-氨基喹啉叠氮锌金属配合物及其制备方法和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113718338A (zh) * | 2021-09-07 | 2021-11-30 | 辽宁石油化工大学 | 一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用 |
| CN113718338B (zh) * | 2021-09-07 | 2023-11-17 | 辽宁石油化工大学 | 一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用 |
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