Supramolecular Tessellations by a Rigid Naphthalene Diimide Triangle
Supramolecular Tessellations by a Rigid Naphthalene Diimide Triangle
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DOI：
10.1021/jacs.9b08758
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发表时间：
2019-11-06
影响因子：
15
通讯作者：
Stoddart, J. Fraser
中科院分区：
文献类型：
--
作者：
Beldjoudi, Yassine;Narayanan, Ashwin;Stoddart, J. Fraser
通过[圆心点圆心点圆心点圆心点π]和电荷转移（CT）相互作用对有机多边形进行镶嵌，为构建具有二维拓扑结构的超分子有机电子材料提供了独特的机会。我们探索萘二亚胺基分子三角形（NDI-Delta）二维镶嵌的三维拓扑结构的方法表明，二维分子排列对溶剂和溶质浓度的身份很敏感。利用非卤化溶剂，结合精心剪裁的浓度，通过[圆心点圆心点圆心点π]相互作用，NDI-Delta自组装成二维蜂窝三角形和六边形平铺图案。NDI-Delta与四硫代fulvalene （TTF）的共结晶系统地导致二维镶嵌的形成，这是上层结构导向CT相互作用的结果。不同的溶剂导致不同的包装方式。利用MeCN、CHCl3和CH2Cl2，我们分别鉴定了三组共晶，分别是CT-A、CT-B和CT-C。溶剂调制不仅在控制NDI-Delta:TTF的化学计量比和晶体上层结构中的分子排列方面起着关键作用，而且还可以防止TTF客体在NDI-Delta的空腔内的包涵。将TTF限制在CT- a上层结构的NDI-Delta空腔内，在近红外区观察到较宽的吸收带，从而增强了CT的特性。在CT-B的上层结构中，CHCl3晶格分子建立了一套[Cl中心点中心点中心点Cl]和[Cl中心点中心点中心点S]分子间的相互作用，导致溶剂形成六角形网格，其中NDI-Delta形成三角形网格。在CT-C上层结构中，三个TTF分子自组装，形成了一个超分子等腰三角形TTF- delta，它与NDI-Delta在一个平面上平铺，产生了两个不同多边形的3 + 3蜂窝平铺图案。CT-C的固体光谱研究表明，在2500 nm处存在一个吸收带，根据TDDFT计算，这是由于两个TTF中心点+自由基阳离子和一个中性TTF分子之间的混合价态特征。
Tessellation of organic polygons though [pi center dot center dot center dot pi] and charge-transfer (CT) interactions offers a unique opportunity to construct supramolecular organic electronic materials with 2D topologies. Our approach to exploring the 3D topology of 2D tessellations of a naphthalene diimide-based molecular triangle (NDI-Delta) reveals that the 2D molecular arrangement is sensitive to the identity of the solvent and solute concentrations. Utilization of nonhalogenated solvents, combined with careful tailoring of the concentrations, results in NDI-Delta self-assembling though [pi center dot center dot center dot pi] interactions into 2D honeycomb triangular and hexagonal tiling patterns. Cocrystallization of NDI-Delta with tetrathiafulvalene (TTF) leads systematically to the formation of 2D tessellations as a result of superstructure-directing CT interactions. Different solvents lead to different packing arrangements. Using MeCN, CHCl3, and CH2Cl2, we identified three sets of cocrystals, namely CT-A, CT-B, and CT-C, respectively. Solvent modulation plays a critical role in controlling not only the NDI-Delta:TTF stoichiometric ratios and the molecular arrangements in the crystal superstructures, but also prevents the inclusion of TTF guests inside the cavities of NDI-Delta. Confinement of TTF inside the NDI-Delta cavities in the CT-A superstructure enhances the CT character with the observation of a broad absorption band in the NIR region. In the CT-B superstructure, the CHCl3 lattice molecules establish a set of [Cl center dot center dot center dot Cl] and [Cl center dot center dot center dot S] intermolecular interactions, leading to the formation of a hexagonal grid of solvent in which NDI-Delta forms a triangular grid. In the CT-C superstructure, three TTF molecules self-assemble, forming a supramolecular isosceles triangle TTF-Delta, which tiles in a plane alongside the NDI-Delta, producing a 3 + 3 honeycomb tiling pattern of the two different polygons. Solid-state spectroscopic investigations on CT-C revealed the existence of an absorption band at 2500 nm, which on the basis of TDDFT calculations, was attributed to the mixed-valence character between two TTF center dot+ radical cations and one neutral TTF molecule.