Metal–organic architectures driven by a multifunctional 6-aminouracil spacer: structures, noncovalent interactions, and conductivity,CrystEngComm

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Metal–organic architectures driven by a multifunctional 6-aminouracil spacer: structures, noncovalent interactions, and conductivity
CrystEngComm ( IF 2.6 ) Pub Date : 2019/12/16 , DOI: 10.1039/c9ce01437c
Atanu Purkayastha _{1,

2,

3} , Sourab Dhar _{2,

3,

4} , Suvra Prakash Mondal _{2,

3,

4} , Antonio Franconetti _{5,

6,

7} , Antonio Frontera _{5,

6,

7} , Rakesh Ganguly _{8,

9,

10} , Alexander M. Kirillov _{11,

12,

13,

14,

15} , Tarun Kumar Misra _{1,

2,

3}

Affiliation

Three new coordination polymers, [Na^I(H₂L)(H₂O)₃]_n (1), {[K^I(H₂L)(H₂O)]₈·13H₂O}_n (2), and {[Ni^IINa^I₂(HL)₂(H₂O)₈]·6H₂O}_n (3), were assembled from 1,3-dimethyl-5-(p-sulfonic-phenylazo)-6-aminouracil (H₃L) as a versatile building block. Although azo-coupling reactions generally result in simple azo-compounds, the presence of the sulfonate (–SO₃⁻) group at the ligand frame led to the formation of the Na^I-1D (1) or K^I-3D (2) homometallic coordination polymer with different ligand coordination modes. Moreover, the heterometallic Ni^II/Na^I-1D (3) coordination polymer was obtained while carrying the reaction of 2 with NiCl₂·6H₂O. The structures of the obtained products were fully established by single crystal X-ray diffraction and confirmed by standard methods. Compounds 1 and 3 possess 1D metal–organic chains with the 2C1 topology, whereas 2 features a very complex 3D metal–organic architecture with an unprecedented topology. The computational study for molecular electrostatic potential (MEP) surface energies revealed an important finding, namely a decrease of the π-acidity of the uracil ring upon coordination and a consequent increase of the π-basicity of the phenyl-sulfonate ring, resulting in effective anti-parallel π–π stacking interactions in 1 and 2. Finally, a semi-conductive behavior of the obtained compounds was explored using impedance spectroscopy, revealing the very remarkable conductive properties of 1 (2.2 × 10⁻⁴ S cm⁻¹), which is a far better conductive material than 2 (7.2 × 10⁻⁶ S cm⁻¹) and 3 (4.8 × 10⁻⁷ S cm⁻¹). The obtained products represent the first coordination compounds derived from H₃L. This study contributes to the design of functional coordination polymers driven by still poorly explored 6-aminouracil building blocks.

中文翻译：

多功能6-氨基尿嘧啶间隔子驱动的金属有机结构：结构，非共价相互作用和电导率

三种新的配位聚合物，[Na ^I（H ₂ L）（H ₂ O）₃ ] _n（1），{[K ^I（H ₂ L）（H ₂ O）] ₈ ·13H ₂ O} _n（2），和{[Ni ^II Na ^I₂（HL）₂（H ₂ O）₈ ]·6H ₂ O} _n（3）由1,3-二甲基-5-（对-磺酸-苯偶氮）-6组装而成-氨基尿嘧啶（H ₃L）作为通用构建块。虽然偶氮偶联反应通常导致简单偶氮化合物，磺酸根的存在（-SO ₃^-）基团在配位体框架导致的Na的形成^我-1D（1）或K^我-3D（2）配体配位方式不同的均金属配位聚合物此外，在使2与NiCl ₂ ·6H ₂进行反应的同时，获得了杂金属Ni ^II / Na ^I -1D（3）配位聚合物。O.获得的产物的结构通过单晶X射线衍射完全确定并通过标准方法确认。化合物1和3具有2C1拓扑的一维金属有机链，而化合物2具有非常复杂的3D金属有机结构，具有前所未有的拓扑。分子静电势（MEP）表面能的计算研究显示出一个重要发现，即配位时尿嘧啶环的π酸度降低，以及苯磺酸盐环的π碱度增加，从而产生了有效1和2中的反平行π–π堆积相互作用。最后，使用阻抗谱研究了所得化合物的半导电行为，发现其非常出色的导电性能1（2.2×10 ^-4 S cm ^-1）比2（7.2×10）更好。^-6 S cm ^-1）和3（4.8×10 ^-7 S cm ^-1）。所获得的产物代表了衍生自H ₃ L的第一个配位化合物。这项研究有助于设计功能性配位聚合物，而该聚合物仍由探索不佳的6-氨基尿嘧啶结构单元驱动。

更新日期：2020-02-10

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