Andrea Pizzi, Arun Dhaka, Roberta Beccaria and Giuseppe Resnati
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In this review we discuss how σ-hole and π-hole bonds can break the paradigm of electrostatic repulsion between like-charges and effectively drive the self-assembly of anions into discrete as well as one-, two-, or three-dimensional adducts. σ-Hole and π-hole bonds are the attractive forces between regions of excess electron density in molecular entities (<em>e.g.</em>, lone pairs or π bond orbitals) and regions of depleted electron density that are localized at the outer surface of bonded atoms opposite to the σ covalent bonds formed by atoms (σ-holes) and above and below the planar portions of molecular entities (π-holes). σ- and π-holes can be present on many different elements of the p and d block of the periodic table and the self-assembly processes driven by their presence can thus involve a wide diversity of mono- and di-anions. The formed homomeric and heteromeric adducts are typically stable in the solid phase and in polar solvents but metastable or unstable in the gas phase. 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引用次数: 0
摘要
在识别和自组装过程中,符号相反的电荷之间的静电吸引和符号相同的电荷之间的静电排斥是无处不在、影响深远的现象。然而,最近有研究发现,同号离子之间的特殊吸引力也比较常见。这些作用力足以克服同号离子之间的库仑斥力,从而形成稳定的阴离子⋯阳离子和阳离子⋯阳离子加合物。氢键(HB)可能是最著名的相互作用,它能有效地引导这些反直觉的组装过程。在这篇综述中,我们将讨论σ-孔和π-孔键如何打破同类电荷之间的静电排斥模式,并有效地推动阴离子自组装成离散的以及一维、二维或三维的加合物、σ-孔和π-孔可能存在于元素周期表中 p 和 d 组的许多不同元素上,因此由它们的存在所驱动的自组装过程可能涉及多种单离子和二离子。所形成的同分异构体和异分异构体加合物通常在固相和极性溶剂中都很稳定,但在气相中却很不稳定。在关键的生物药理系统和具有有用功能特性的分子材料中,σ- 和 π-孔键在控制阴离子⋯阴离子自组装中发挥了关键作用。
Anion⋯anion self-assembly under the control of σ- and π-hole bonds
The electrostatic attraction between charges of opposite signs and the repulsion between charges of the same sign are ubiquitous and influential phenomena in recognition and self-assembly processes. However, it has been recently revealed that specific attractive forces between ions with the same sign are relatively common. These forces can be strong enough to overcome the Coulomb repulsion between ions with the same sign, leading to the formation of stable anion⋯anion and cation⋯cation adducts. Hydroden bonds (HBs) are probably the best-known interaction that can effectively direct these counterintuitive assembly processes. In this review we discuss how σ-hole and π-hole bonds can break the paradigm of electrostatic repulsion between like-charges and effectively drive the self-assembly of anions into discrete as well as one-, two-, or three-dimensional adducts. σ-Hole and π-hole bonds are the attractive forces between regions of excess electron density in molecular entities (e.g., lone pairs or π bond orbitals) and regions of depleted electron density that are localized at the outer surface of bonded atoms opposite to the σ covalent bonds formed by atoms (σ-holes) and above and below the planar portions of molecular entities (π-holes). σ- and π-holes can be present on many different elements of the p and d block of the periodic table and the self-assembly processes driven by their presence can thus involve a wide diversity of mono- and di-anions. The formed homomeric and heteromeric adducts are typically stable in the solid phase and in polar solvents but metastable or unstable in the gas phase. The pivotal role of σ- and π-hole bonds in controlling anion⋯anion self-assembly is described in key biopharmacological systems and in molecular materials endowed with useful functional properties.
期刊介绍:
Chemical Society Reviews is published by: Royal Society of Chemistry.
Focus: Review articles on topics of current interest in chemistry;
Predecessors: Quarterly Reviews, Chemical Society (1947–1971);
Current title: Since 1971;
Impact factor: 60.615 (2021);
Themed issues: Occasional themed issues on new and emerging areas of research in the chemical sciences