The halogen bond in the design of functional supramolecular materials: recent advances.
The halogen bond in the design of functional supramolecular materials: recent advances.
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DOI：
10.1021/ar400103r
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发表时间：
2013-11-19
影响因子：
18.3
通讯作者：
Resnati, Giuseppe
中科院分区：
文献类型：
--
作者：
Priimagi, Arri;Cavallo, Gabriella;Metrangolo, Pierangelo;Resnati, Giuseppe
卤素键是构建超分子组装的一种新兴的非共价相互作用。虽然类似于更常见的氢键，但这两种相互作用之间的四个主要区别使卤素键成为分子识别和功能材料设计的独特工具。首先，卤素键往往比(单一)氢键更具方向性。其次，相互作用的强度与键供体原子的极化率成比例，研究人员可以通过单原子突变来调整这一特征。此外，卤素键是疏水的，而氢键是亲水的。最后，给键原子(卤素)的尺寸比氢大得多。因此，卤素键合为超分子化学家提供了其他类型的非共价相互作用难以满足的设计工具，并为智能功能材料的设计开辟了前所未有的可能性。本文着重介绍了卤素键基功能材料设计的最新进展。卤素成键、方向性、可调的相互作用强度、疏水性和大施主原子尺寸等每一种独特的特征都会产生不同的影响。利用这种疏水性，研究人员设计了小型离子转运体。大的卤素原子尺寸为构建高效产生三重态电子并具有高磷光量子产率的全有机发光晶体提供了平台。可调节的相互作用强度为理解光响应性偶氮苯聚合物中的光诱导宏观运动提供了工具，而方向性使得卤素键在功能超分子液晶和凝胶相材料的设计中非常有用。虽然卤素键基功能材料的设计还处于起步阶段，但我们可以预见这一领域的光明前景。我们期待基于卤素键设计的材料可以在仿生学、光学/光子学、功能表面和可光切换的超分子中得到应用。
Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials. This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to applications in biomimetics, optics/photonics, functional surfaces, and photoswitchable supramolecules.
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