CN113278031A - 一种铜基纳米团簇、离子液体诱导合成方法以及应用 - Google Patents
一种铜基纳米团簇、离子液体诱导合成方法以及应用 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 8
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims abstract description 11
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- -1 amine salt Chemical class 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 230000006698 induction Effects 0.000 claims abstract 2
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- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims 1
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- UDLLFLQFQMACJB-UHFFFAOYSA-N azidomethylbenzene Chemical compound [N-]=[N+]=NCC1=CC=CC=C1 UDLLFLQFQMACJB-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
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- 208000012839 conversion disease Diseases 0.000 description 3
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- SVABQOITNJTVNJ-UHFFFAOYSA-N diphenyl-2-pyridylphosphine Chemical compound C1=CC=CC=C1P(C=1N=CC=CC=1)C1=CC=CC=C1 SVABQOITNJTVNJ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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Abstract
本发明属于无机‑有机纳米材料技术领域，具体为一种制备新型二腈胺和二苯基‑2‑吡啶膦（Dppy）双配体保护的铜纳米簇合物晶体{Cu12H9(Dppy)6[N(CN)2]3}的合成方法。通过“从团簇到团簇”的方法，利用1‑乙基‑3‑甲基咪唑二腈胺盐离子液体诱导已报道的原子精确的铜纳米团簇[Cu7H5(Dppy)6](ClO4)2在二氯甲烷溶剂中发生结构重组，而后采用乙醚扩散结晶4‑5天即可得到。与现有合成铜纳米簇技术的对比，本发明方法具有合成方法简便，反应条件温和、反应时间短和纯化简单等优点；并且该铜纳米晶体具有优良的发光性能和较高的Click反应的催化活性，在发光器件和催化反应中具有潜在的应用。
Description
技术领域
本发明属于金属纳米簇化合物技术领域，具体涉及一种铜基纳米团簇、离子液体诱导合成方法以及应用。
背景技术
近些年来，原子精确的贵金属纳米团簇因其多样的结构、良好的光物理化学性能以及尺寸效应而备受关注。相比于同类的金、银纳米团簇，铜纳米团簇因其价格低廉，易于获得，作为稀有金属和贵金属的替代金属材料在催化，化学传感器，药物，能量存储，抗菌等领域具有十分广阔的应用前景而备受关注。在铜纳米团簇的设计合成过程中，功能性有机配体的选择以及不同的制备方法对铜纳米团簇的结构起着至关重要的作用。现公开发表的铜纳米簇大部分选择结构简单的含硫、磷的配体，合成得到的纳米团簇的光物理化学性能较差。而且已报道的铜基纳米团簇的合成大多采用直接还原简单铜盐和硫、磷的配体的方法，反应条件需要绝氧，反应条件较为苛刻，其副产物不利于环境友好，大多数产物产率较低，而且得到的铜纳米团簇往往结构不可控，稳定性较差。因此，探究一种全新便捷的方法合成具有独特性能的铜纳米团簇具有重要的研究意义。
发明内容
本发明的目的在于提供一种铜基纳米团簇、离子液体诱导合成方法以及应用。本发明的铜纳米晶体具有独特的十四面体笼状结构，具有优良的发光性能和较高的Click反应的催化活性，在发光器件和催化反应中具有潜在的应用。
为实现上述目的，本发明采用如下技术方案：
本发明采用一种 “从团簇到团簇”的离子液体诱导合成一种新型二腈胺([N(CN)2]-)和二苯基-2-吡啶膦（Dppy）双配体保护的铜纳米簇晶体{Cu12H9(Dppy)6[N(CN)2]3}的新方法，具体合成过程见图1。
具体为利用1-乙基-3-甲基咪唑二腈胺盐离子液体诱导铜纳米团簇[Cu7H5(Dppy)6](ClO4)2在二氯甲烷溶剂中发生结构重组反应，而后采用乙醚扩散结晶方法即可得到。具体步骤为：
在试管中将[Cu7H5(Dppy)6](ClO4)2溶于CH2Cl2，在溶液上方中滴入 Cu7簇用量60倍摩尔当量的1-乙基-3-甲基咪唑二腈胺盐，而后向溶液上层滴加乙醚，在30 ℃下4 - 5天扩散，获得红色不规则晶体{Cu12H9(Dppy)6[N(CN)2]3}。
进一步地，1-乙基-3-甲基咪唑二腈胺盐加入量为[Cu7H5(Dppy)6](ClO4)2用量的60倍摩尔当量。
进一步地，CH2Cl2与乙醚体积比为1：2。
进一步地，[Cu7H5(Dppy)6](ClO4)2在二氯甲烷CH2Cl2溶剂的浓度为8-10 mol/L.
其中铜纳米团簇[Cu7H5(Dppy)6](ClO4)2是参考专利文献（CN107652311B）合成。
进一步地，本发明的铜纳米簇晶体具有独特的十四面体笼状结构；其晶体具有优良的发光性能，用395 -430 nm的激发波长激发，其展现出红光发射，最强发射峰在690 nm；该铜纳米簇可用于高效催化苄基叠氮和苯乙炔的Click反应（见图2），在二氯甲烷溶剂中，{Cu12H9(Dppy)6[N(CN)2]3}簇为0.4 mol%的催化用量时，反应时间为150 min，苄基叠氮和苯乙炔的Click反应转化率可达到92.3 %，相比于其他铜簇，其催化速率显著提升。
本发明的显著优点在于：
相较于目前已报道的合成铜纳米团簇方法，本方法具有合成步骤简便，反应条件温和、反应时间短和纯化简单等优点。本发明得到的铜纳米晶体{Cu12H9(Dppy)6[N(CN)2]3}在空气中的稳定性较好，可以在低温环境下储存数月。 铜纳米晶体{Cu12H9(Dppy)6[N(CN)2]3}具有独特的十四面体笼状结构，具有优良的发光性能和较高的Click反应的催化活性，在发光器件和催化反应中具有潜在的应用。
附图说明
图1 铜纳米簇晶体{Cu12H9(Dppy)6[N(CN)2]3}的合成路线；
图2 铜纳米簇晶体{Cu12H9(Dppy)6[N(CN)2]3}催化Click反应路线图。
图3 铜纳米簇晶体{Cu12H9(Dppy)6[N(CN)2]3}催化Click反应转化率随时间变化图。
具体实施方式
为进一步公开而不是限制本发明，以下结合实例对本发明作进一步的详细说明。
实施例 新型铜纳米簇晶体{Cu12H9(Dppy)6[N(CN)2]3}的制备
在试管中将[Cu7H5(Dppy)6](ClO4)2（111 mg，0.05 mmol）溶于6 mL CH2Cl2，在溶液上方中滴入500 μL 1-乙基-3-甲基咪唑二腈胺盐，而后向溶液上层滴加12 mL的乙醚，在30℃下4 - 5天扩散即可获得红色不规则晶体{Cu12H9(Dppy)6[N(CN)2]3}，平均产率为25－30%（产率以Cu的含量计算）。
{Cu12H9(Dppy)6[N(CN)2]3}簇化学式：C108H93Cu12N15P6
元素分析：计算值 (实验值)(%)：C: 50.88 (49.05)；H: 3.68 (3.56)；N: 8.24(9.74).
红外吸收主要特征峰(KBr, ν / cm-1): 2250 (-C≡N); 1569，1476，1435 (Dppy苯环C-C、吡啶环C-N) .
1H NMR (400 MHz, CD2Cl2, δ, ppm): 8.60 (s, 1H), 7.88 (s, 1H), 7.71 (s,8H), 7.35 (s, 4H) .
31P{1H} NMR (400MHz, CD2Cl2,δ, ppm): -6.59 (s).
电子能谱分析(XPS)： 952.4 ev (Cu 2P1/2)，932.5 eV (Cu 2P3/2); 399.8 eV (N1s); 284.8 eV (C 1s); 131.7 eV (P 2p).
电喷雾质谱ESI-MS [m/z (%)]: 783.58 (13) [Cu12H9(Dppy)6]3+；589.10 (100)[Cu(Dppy)2]+。
晶体学数据：Triclinic, P-1, a = 15.0012(7) (Ǻ), b = 15.2486(7) (Ǻ),c = 25.4308(12) (Ǻ); α = 83.616(2) (˚), β = 81.295(2) (˚), γ = 72.839(2)(˚), V = 5480.6(5)。
应用例 铜纳米簇晶体{Cu12H9(Dppy)6[N(CN)2]3}催化Click反应
催化反应线路图如图2所示，反应在Schlenk技术氮气条件下进行。向25 mL反应瓶中依次加入苯乙炔（137 μL，1.1 mmol）、苄基叠氮（113 μL，1 mmol）以及{Cu12H9(Dppy)6[N(CN)2]3}（4 μmol，0.4 mol%）以及2.5 mL CH2Cl2。搅拌反应，用GC-MS检测反应进程和产物1-苄基-4-苯基-1H-1,2,3-三唑化物的含量。实验结果表明反应时间为150 min，苄基叠氮和苯乙炔的Click反应转化率可达到92.3 %（见图3），而同等条件下不添加催化剂，转化率低于10%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (8)
1.一种铜基纳米团簇的合成方法，其特征在于：通过“从团簇到团簇”的方法，利用1-乙基-3-甲基咪唑二腈胺盐离子液体诱导铜纳米团簇[Cu7H5(Dppy)6](ClO4)2在二氯甲烷溶剂中发生结构重组，而后采用乙醚扩散结晶4-5天得到二腈胺和二苯基-2-吡啶膦Dppy双配体保护的铜纳米簇合物晶体{Cu12H9(Dppy)6[N(CN)2]3}。
2.根据权利要求1所述的合成方法，其特征在于：在试管中将[Cu7H5(Dppy)6](ClO4)2溶于CH2Cl2，在溶液上方中滴入 1-乙基-3-甲基咪唑二腈胺盐，而后向溶液上层滴加乙醚，在30 ℃下4 - 5天扩散，获得红色不规则晶体。
3.根据权利要求2所述的合成方法，其特征在于：1-乙基-3-甲基咪唑二腈胺盐加入量为[Cu7H5(Dppy)6](ClO4)2用量的60倍摩尔当量。
4.根据权利要求2所述的合成方法，其特征在于：CH2Cl2与乙醚体积比为1：2。
5.根据权利要求2所述的合成方法，其特征在于：[Cu7H5(Dppy)6](ClO4)2在CH2Cl2的浓度为8-10 mol/L。
6.一种如权利要求1-5任一项所述合成方法获得的铜基纳米团簇。
7.根据权利要求6所述的铜基纳米团簇在发光器件上的应用。
8.根据权利要求6所述的铜基纳米团簇在催化反应上的应用。
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