CN112625068B - 一种异双核镍铕配合物的制备、结构及荧光 - Google Patents
一种异双核镍铕配合物的制备、结构及荧光 Download PDFInfo
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- RSTMBJAUVCMABY-UHFFFAOYSA-N europium nickel Chemical compound [Ni][Eu] RSTMBJAUVCMABY-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- UOJZYBFRNITHCX-UHFFFAOYSA-N 2,3,5,6-tetrapyridin-2-ylpyrazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=C(C=2N=CC=CC=2)N=C1C1=CC=CC=N1 UOJZYBFRNITHCX-UHFFFAOYSA-N 0.000 claims abstract description 5
- IUEQMQXAVZARKU-UHFFFAOYSA-N 2-pyridin-2-ylpyrazine Chemical compound N1=CC=CC=C1C1=CN=CC=N1 IUEQMQXAVZARKU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 4
- -1 Rare earth ion Chemical class 0.000 claims abstract description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 2
- 230000009920 chelation Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明公开了一种基于2′3′5′6‑四(2‑吡啶基)吡嗪的异双核镍铕配合物的制备、结构及其荧光。所述配合物的化学式为：[Ni(tppz)2][Eu(NO3)5]·CH3CN(式中tppz为2′3′5′6‑四(2‑吡啶基)吡嗪)。该配合物属于正交晶系，P21/c空间群，其最小结构单元包含一个Eu3+稀土离子，一个Ni2+过渡金属离子，二个三齿螯合的2,3,5,6‑四(2‑吡啶基)吡嗪(tppz)和五个NO3‑离子。465nm激发，该配合物在618(5D0→7F2)nm处出现铕中心的特征亮红色荧光发射，其CIE值为(0.6894，0.3105)。
Description
技术领域
本发明属于配合物性质研究技术领域，涉及一种基于2′3′5′6-四(2-吡啶基)吡嗪的异双核镍铕配合物的制备、结构及其荧光。
背景技术
目前配位化学已经成为一个非常活跃研究领域，具有较大共轭体系的2′3′5′6-四(2-吡啶基)吡嗪(tppz)，是一种非常具有吸引力的“背靠背”式三联吡啶类配体，具有三齿螯合的配位点，一端可以和过渡金属配位，另一端可以和稀土离子螯合，最后组装成d-f发光体系。该配体在分子内有6个含N配位点，能与金属离子配位形成稳定的五元螯合环。在磁学、光物理、光化学、电化学上表现出优良性质，在超分子化学、功能材料上具有广泛的应用前景。
发明内容
本发明的目的：提供一种基于2′3′5′6-四(2-吡啶基)吡嗪的异双核镍铕配合物的制备、结构及荧光。
本发明的思路：采用tppz配体与Ni(NO3)2·6H2O通过溶液法获得[Ni(tppz)2](NO3)2,然后采用[Ni(tppz)2](NO3)2与Eu(NO3)3·6H2O通过溶剂热法合成异双核镍铕配合物。
异双核镍铕配合物配合物的结构见附图1。本发明所述配合物的化学式为：[Ni(tppz)2][Eu(NO3)5]·CH3CN(式中tppz为2′3′5′6-四(2-吡啶基)吡嗪)。该配合物属于正交晶系，空间群为P21/c，晶胞参数为a＝14.2256(4)，b＝18.3932(5)，c＝22.3880(6)，α＝90°，β＝103.501(3)，γ＝90°，V＝5696.1(3)。
上述配合物的荧光性质研究：
配合物的室温固态荧光光谱图见附图2。465nm激发，该配合物在618(5D0→7F2)nm处出现铕中心的特征亮红色荧光发射，其CIE值为(0.6894，0.3105)。
上述铕配合物的制备方法如下：
将2′3′5′6-四(2-吡啶基)吡嗪(tppz)(155.0mg，0.400mmol)溶于16mL二氯甲烷中，向其中缓慢滴加8mL Ni(NO3)2·6H2O(58.2mg，0.200mmol)乙醇溶液，得黄褐色的澄清溶液。室温下剧烈搅拌24h，放置3～4天，有黄褐色的[Ni(tppz)2](NO3)2晶体析出。冷乙醇反复清洗晶体2～3次，干燥备用。称取制得的[Ni(tppz)2](NO3)2(47.9mg，0.050mmol)溶于15mL乙腈，向其中缓慢滴加4mL Eu(NO3)3·6H2O(44.6mg，0.100mmol)乙腈溶液，室温下混合均匀后转移至25mL的反应釜内。封釜，120℃烧釜两天后进行梯度降温至室温，开釜，得到适于X-ray单晶解析的淡黄色晶体[Ni(tppz)2][Eu(NO3)5]·CH3CN。乙腈冲洗3次，干燥，产率为87％。
附图说明
图1是本发明的异双核镍铕配合物分子结构图。
图2是本发明的异双核镍铕配合物固态荧光光谱图。
图3图是本发明的异双核镍铕配合物CIE色度坐标。
具体实施方式
该配合物属于正交晶系，空间群为P21/c，晶胞参数为a＝14.2256(4)，b＝18.3932(5)，c＝22.3880(6)，α＝90°，β＝103.501(3)，γ＝90°，V＝5696.1(3)。该配合物的最小结构单元包含一个Eu3+稀土离子，一个Ni2+过渡金属离子，二个三齿螯合的2,3,5,6-四(2-吡啶基)吡嗪(tppz)和五个NO3-离子。其中二个中性配体2,3,5,6-四(2-吡啶基)吡嗪(tppz)以六个N原子(N4，N5，N6，N7，N8，N9)与Ni2+螯合，形成六配位的变型八面体构型；五个双齿螯合的NO3-分别以与Eu3+形成十配位的双帽十二面体构型。
Claims (3)
1. 一种异双核镍铕配合物，其特征在于：所述配合物的化学式为：[Ni(tppz)2][Eu(NO3)5]·CH3CN，式中tppz为2′3′5′6-四(2-吡啶基)吡嗪；所述的异双核镍铕配合物的制备方法，其特征在于：将155.0 mg，0.400 mmol 的2′3′5′6-四(2-吡啶基)吡嗪溶于16 mL二氯甲烷中，向其中缓慢滴加8 mL 含58.2 mg，0.200 mmol Ni(NO3)2·6H2O的乙醇溶液，得黄褐色的澄清溶液；室温下剧烈搅拌24 h，放置3~4天，有黄褐色的[Ni(tppz)2](NO3)2晶体析出；冷乙醇反复清洗晶体2~3次，干燥备用；称取制得的47.9 mg，0.050 mmol 的[Ni(tppz)2](NO3)2溶于15 mL乙腈，向其中缓慢滴加4 mL 含44.6 mg，0.100 mmol Eu(NO3)3·6H2O的乙腈溶液，室温下混合均匀后转移至25 mL的反应釜内；封釜，120°C烧釜两天后进行梯度降温至室温，开釜，得到适于X-ray单晶解析的淡黄色晶体[Ni(tppz)2][Eu(NO3)5]·CH3CN；乙腈冲洗3次，干燥，产率为87%。
2.根据权利要求1所述的异双核镍铕配合物，其特征在于：该配合物属于单斜晶系，空间群为P21/c，晶胞参数为a = 14.2256(4)，b = 18.3932(5)，c = 22.3880(6)，α = 90°，β= 103.501(3)，γ = 90°，V = 5696.1(3)；该配合物的最小结构单元包含一个Eu3+稀土离子，一个Ni2+过渡金属离子，二个三齿螯合的2,3,5,6-四(2-吡啶基)吡嗪中性配体和五个NO3-离子；其中二个中性配体2,3,5,6-四(2-吡啶基)吡嗪以六个N原子，具体为N4、N5、N6、N7、N8和N9与Ni2+离子六齿螯合，形成六配位的变型八面体构型；五个双齿螯合NO3-分别与Eu3+形成十配位的双帽十二面体构型。
3.根据权利要求1所述的异双核镍铕配合物，其荧光性能及应用特征在于：在465 nm激发下，该配合物在618 nm处出现铕中心的5D0→7F2特征亮红色荧光发射，其CIE值为(0.6894，0.3105)；荧光性质研究表明其在荧光材料领域可得以应用。
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