Strain-Induced Helical Chirality in Polyaromatic Systems Cite This: Chem
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Chem Soc Rev View Article Online TUTORIAL REVIEW View Journal | View Issue Strain-induced helical chirality in polyaromatic systems Cite this: Chem. Soc. Rev., 2016, 45,1542 a abc a Michel Rickhaus, Marcel Mayor* and Michal Jurı´cˇek Helicity in a molecule arises when the molecule contains a stereogenic axis instead of a stereogenic centre. In a molecule that is not inherently helically chiral, helicity can be induced by designing the molecule such that an unfavourable steric interaction, or strain, is present in its planar conformation. The release of this strain forces the molecule to adopt a helical twist against the cost of the torsional strain induced in the backbone, an interplay of forces, which must be balanced in favour of the helical conformation over the planar one. In this tutorial review, design principles that govern this process are analysed and the selected examples are categorised into three main (I, II and III) and two related (IV and V) classes, simply by their relation to one of the three types of helically twisted ribbons or two types of helically Received 10th August 2015 twisted cyclic ribbons, respectively. The presented examples were selected such that they illustrate their Creative Commons Attribution 3.0 Unported Licence. DOI: 10.1039/c5cs00620a category in the best possible way, as well as based on availability of their solid-state structures and racemisation energy barriers. Finally, the relationship between the structure and properties is discussed, www.rsc.org/chemsocrev highlighting the cases in which induced helicity gave rise to unprecedented phenomena. Key learning points (1) Chirality can arise without stereogenic centres. (2) Strain introduced into a sufficiently rigid backbone can induce helical chirality. (3) Linked or fused aromatic rings are ideally suited to relay helicity within a structure. This article is licensed under a (4) Strained helical molecules often show surprisingly low racemisation barriers and are more flexible than is generally believed. (5) Helicity induced in a p-conjugated system often leads to an unusual electronic structure and unexpected properties. Open Access Article. Published on 14 January 2016. Downloaded 17/05/2016 12:00:21. 1. Introduction Helical chirality is a property of chiral systems3 that do not contain stereogenic centres, that is, asymmetric units Since its elucidation in 1953, the double-helix structure of DNA where four non-equivalent points represent the vertices of a has fostered the role that chirality plays1 in living systems, tetrahedron. In a helical stereogenic unit, four points that can namely, providing function with complexity. Helical chirality, be identical are placed in a three-dimensional space such that in particular, governs2 formation of many supramolecular the system is not superimposable on its mirror image. This type assemblies composed of chiral or even achiral molecular build- of chirality is also known as axial chirality because of the ing blocks in both biological and artificial systems. The helical presence of a stereogenic axis instead of a centre. In molecules secondary structure often defines the function of complex that are not inherently helically chiral, helicity can be induced. assemblies beyond a single stereogenic centre and translates Flexible molecules, such as DNA, can be folded into a helical chirality from the molecular level to the nanometer scale. conformation by specific directional non-covalent interactions, for Understanding how complexity arises from simple building example, hydrogen bonding. In rigid molecules, helical conforma- blocks and the role of chirality in this process is the key to tions can arise if unfavourable steric interactions, or strain, are the design of functional systems. present in their non-helical conformations, which is the driving force towards formation of the energetically favoured helical conformations. This second type of helical chirality, here referred a Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, to as strain-induced, is the subject of this tutorial review. Switzerland. E-mail: [email protected] The helical conformation is induced4 by minimising the b Institute for Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), P. O. Box 3640, 76021 Karlsruhe, Germany steric interactions present in the planar conformation against the c Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, energy cost of the torsional strain, or deformation, induced upon Guangzhou, P. R. China twisting the molecule. The main requirement for a molecule to 1542 | Chem. Soc. Rev., 2016, 45, 1542--1556 This journal is © The Royal Society of Chemistry 2016 View Article Online Tutorial Review Chem Soc Rev adopt a helical conformation is therefore the right balance of of induced strain, structural and dynamic parameters are discussed the two forces, the first one being the driving force. As a in detail. Therefore, compounds, whose solid-state structures as consequence, it is necessary that the molecule is both rigid well as the Gibbs free energy barriers (DG‡) of racemisation are and flexible at the same time. Fused or linked polyaromatic available, were selected preferentially. In the case of less recent systems are ideally suited to serve this purpose because their examples, the DG‡ values were estimated from the activation core is sufficiently rigid. In parallel, the induced deformation is energies (Ea) of racemisation and the corresponding A values, typically spread over a large number of bonds, which makes the using the Arrhenius and Eyring equations. In addition, we have core relatively flexible. Conceptually different types of strain- tried to include as many recent significant examples as possible, induced polyaromatic helices have been reported in the literature. which have not been reviewed before. These numerous significant achievements notwithstanding, there Fig. 1 illustrates three limiting cases of twisting a ribbon is still intellectual space left for designing conceptually new helical with edges highlighted in black and blue for clarity. Depending systems, which are induced by strain and which adopt well- on the position of the stereogenic axis, three types, namely, I, defined geometries. Understanding how helicity arises and how II and III, can be recognised. A type I helical ribbon coils around it is translated into properties in these systems is crucial for an axis, which does not have an intersection with the ribbon, understanding the interplay between chirality and function. leading to a structure reminiscent of a staircase. As a result, the It is important to note that numerous examples are known blue and black edges do not have the same length, the blue edge in the literature, many of which could not be included in this being consistently the longer one in this review (except for the review because of space restrictions. As most of these have case of equal lengths of the two edges). Molecular analogues are recently been reviewed exhaustedly, we focused on the qualita- known as helicenes (Section 2), the most archetypal examples of tive rather than quantitative analysis and classification of the helical polyaromatic systems. The steric interaction between selected examples. Previous reviews on helically chiral strained overlapping or partially overlapping rings forces helicenes to polyaromatic compounds include four recent, extensive reviews adopt a helical conformation against the energy cost of the 5–7 8 9 Creative Commons Attribution 3.0 Unported Licence. on [n]helicenes and twistacenes and one other review torsional strain induced in the helicene backbone. highlighting specific examples. Each review, however, deals mostly Type II features a stereogenic axis that is identical to the with one class of helical molecules and focuses on different main axis of the untwisted, planar ribbon. When the ribbon is synthetic approaches, including stereoselective synthesis, to these twisted around this axis, both edges have the same length and targets. A general concept bringing all the structural motifs together are pirouetting around the axis similarly to the strands of in a systematic way has been missing in the literature and is double-helix DNA. The closest molecular analogues of type II addressed in this conceptual review. The strain-induced helical ribbon are known as twistacenes (Section 3). Unfavourable steric architectures are organised by means that they adopt a helical interactions are achieved by introducing steric crowdedness conformation, and their structural design and its consequences are around the periphery. The energy benefit of minimising these This article is licensed under a discussed. Because of the vast number of examples, the presented steric interactions is optimised against the energy cost of structures were selected thoroughly, such that they illustrate the distorting the p-system from planarity. differences between various types of strain-induced helical systems In type III, the stereogenic axis and the black edge of a ribbon, Open Access Article. Published on 14 January 2016. Downloaded 17/05/2016 12:00:21. as clearly and simply as possible. To qualitatively assess the amount instead of the main axis of its planar form, are identical. Michel Rickhaus obtained his MSc (2011) and PhD (2015) from the University of Basel under the supervision of Professor Marcel Mayor. His research interests involve the development of new concepts for inducing twists and strain in aromatic materials. Under the supervision