Zn（II）和Cd（II）在具有多价曼尼希碱配体的配合物中对核的调节：Zn（II）的开启发光传感器和Zn（II）配合物检测硝基芳烃炸药,Crystal Growth & Design

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Zn（II）和Cd（II）在具有多价曼尼希碱配体的配合物中对核的调节：Zn（II）的开启发光传感器和Zn（II）配合物检测硝基芳烃炸药
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2018-03-10 00:00:00 , DOI: 10.1021/acs.cgd.7b01752
Avijit Das ₁ , Subrata Jana ₁ , Ashutosh Ghosh ₁

Affiliation

Zn（II）离子与配体H ₂ L（H ₂ L = N，N'-二甲基-N，N'-双（2-羟基-3-甲氧基-5-甲基苄基）乙二胺）的反应桥接大分子大分子，氯化物，硫氰酸盐/乙酸盐或叠氮化物/乙酸盐会生成三种新的双核络合物，[Zn ₂ LCl ₂（H ₂ O）]（1），[Zn ₂ L（SCN）₂（H ₂ O）]·H ₂ O（2）和[Zn ₂ L（N ₃）（CH ₃ CO ₂）]（3），而Cd（II）离子形成了三个新的四核配合物，[Cd ₄ L ₂ Cl ₄ ]·H ₂ O（4），[Cd ₄ L ₂（SCN）₂（CH ₃ CO ₂）₂ ]·2H ₂ O（5）和[Cd ₄ L ₂（N ₃）₂（CH ₃ CO ₂）₂ ]·3H ₂ O（6）具有相同的配体和大分子配体。Zn（II）离子在其所有配合物中均经过五配位1– 3，但配合物3中的一个锌中心是扭曲的四面体。其配合物4和5中的所有四个Cd（II）中心均具有六配位扭曲的八面体几何形状。在复合物6中，两个Cd（II）中心是六配位的，其他两个是七配位的。去质子化的配体（L ^2-）是六- /庚齿状在锌（II）配合物，1 - 3但辛齿状在CD ^II络合物4 - 6。考虑到对这两种金属离子的不同配位数的偏好，已经解释了所得络合物中核度和配体配位方式的差异。H ₂ L对Zn ²⁺离子具有高度特异性，灵敏性和选择性的开启荧光感应特性。还计算了荧光增强的机理，宿主客体结合化学计量和结合常数。Zn ²⁺离子的检出限为7.69 nM，结合常数K = 1.508×10 ¹⁰ M ^–2。产生的Zn（II）配合物通过关闭荧光反应感应溶液中的硝基芳香族炸药。解决方案相位感测机制已进行了深入研究。值得注意的是，检测苦味酸在ppt级的（912，910，和896个百分点为复合物的极限1，2，和3分别地）具有强淬灭常数（ķ _SV）为8.063×10 ⁴，7.987×10 ⁴，和8.51×10 ⁴中号^-1复杂1，2，和3分别。

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Modulation of Nuclearity by Zn(II) and Cd(II) in Their Complexes with a Polytopic Mannich Base Ligand: A Turn-On Luminescence Sensor for Zn(II) and Detection of Nitroaromatic Explosives by Zn(II) Complexes

Reactions of Zn(II) ion with the ligand H₂L (H₂L = N,N′-dimethyl-N,N′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)ethylenediamine) in the presence of bridging coligands, chloride, thiocyanate/acetate, or azide/acetate yielded three new dinuclear complexes, [Zn₂LCl₂(H₂O)] (1), [Zn₂L(SCN)₂(H₂O)]·H₂O (2), and [Zn₂L(N₃)(CH₃CO₂)] (3), whereas Cd(II) ion formed three new tetranuclear complexes, [Cd₄L₂Cl₄]·H₂O (4), [Cd₄L₂(SCN)₂(CH₃CO₂)₂]·2H₂O (5), and [Cd₄L₂(N₃)₂(CH₃CO₂)₂]·3H₂O (6) with the same ligand and coligands. The Zn(II) ions are penta-coordinated in all of its complexes 1–3 except one zinc center in complex 3, which is distorted tetrahedral. All four Cd(II) centers in each of its complexes 4 and 5 possess hexa-coordinated distorted octahedral geometry. In complex 6, two Cd(II) centers are hexa-coordinated, and the other two are hepta-coordinated. The deprotonated ligand (L^2–) is hexa-/hepta-dentate in the Zn(II) complexes, 1–3 but octa-dentate in the Cd^II complexes 4–6. The differences in nuclearity and in the coordination modes of the ligands in the resulting complexes have been explained considering the preference for different coordination numbers of these two metal ions. H₂L exhibited highly specific, sensitive, and selective turn-on fluorescence sensing properties for the Zn²⁺ ion. The mechanism of fluorescence enhancement, host guest binding stoichiometry, and binding constant has also been calculated. The detection limit of Zn²⁺ ion is 7.69 nM, with the binding constant K = 1.508 × 10¹⁰ M^–2. The produced Zn(II) complexes sense nitroaromatic explosives in solution via a turn-off florescence response. The solution phase sensing mechanism has been studied thoroughly. Remarkably, the limit of detection of picric acid at the ppt level (912, 910, and 896 ppt for complexes 1, 2, and 3 respectively) having a strong quenching constant (K_SV) is 8.063 × 10⁴, 7.987 × 10⁴, and 8.51 × 10⁴ M^–1 for complex 1, 2, and 3 respectively.

更新日期：2018-03-10

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