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      An unforeseen polymorph of coronene by the application of magnetic fields during crystal growth

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          Abstract

          The continued development of novel drugs, proteins, and advanced materials strongly rely on our ability to self-assemble molecules in solids with the most suitable structure (polymorph) in order to exhibit desired functionalities. The search for new polymorphs remains a scientific challenge, that is at the core of crystal engineering and there has been a lack of effective solutions to this problem. Here we show that by crystallizing the polyaromatic hydrocarbon coronene in the presence of a magnetic field, a polymorph is formed in a β-herringbone structure instead of the ubiquitous γ-herringbone structure, with a decrease of 35° in the herringbone nearest neighbour angle. The β-herringbone polymorph is stable, preserves its structure under ambient conditions and as a result of the altered molecular packing of the crystals, exhibits significant changes to the optical and mechanical properties of the crystal.

          Abstract

          Polymorphism, the presence of different crystal structures of the same molecular system, provides an opportunity to discover new phenomena and properties. Here, the authors crystallize coronene in the presence of a magnetic field, forming a different polymorph, which remains stable under ambient conditions.

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          Most cited references8

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          Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data.

          We present a parameter-free method for an accurate determination of long-range van der Waals interactions from mean-field electronic structure calculations. Our method relies on the summation of interatomic C6 coefficients, derived from the electron density of a molecule or solid and accurate reference data for the free atoms. The mean absolute error in the C6 coefficients is 5.5% when compared to accurate experimental values for 1225 intermolecular pairs, irrespective of the employed exchange-correlation functional. We show that the effective atomic C6 coefficients depend strongly on the bonding environment of an atom in a molecule. Finally, we analyze the van der Waals radii and the damping function in the C6R(-6) correction method for density-functional theory calculations.
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            Selection of supramolecular chirality by application of rotational and magnetic forces.

            Many essential biological molecules exist only in one of two possible mirror-image structures, either because they possess a chiral unit or through their structure (helices, for example, are intrinsically chiral), but so far the origin of this homochirality has not been unraveled. Here we demonstrate that the handedness of helical supramolecular aggregates formed by achiral molecules can be directed by applying rotational, gravitational and orienting forces during the self-assembly process. In this system, supramolecular chirality is determined by the relative directions of rotation and magnetically tuned effective gravity, but the magnetic orientation of the aggregates is also essential. Applying these external forces only during the nucleation step of the aggregation is sufficient to achieve chiral selection. This result shows that an almost instantaneous chiral perturbation can be transferred and amplified in growing supramolecular self-assemblies, and provides evidence that a falsely chiral influence is able to induce absolute enantioselection.
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              Polymorphism control of superconductivity and magnetism in Cs(3)C(60) close to the Mott transition.

              The crystal structure of a solid controls the interactions between the electronically active units and thus its electronic properties. In the high-temperature superconducting copper oxides, only one spatial arrangement of the electronically active Cu(2+) units-a two-dimensional square lattice-is available to study the competition between the cooperative electronic states of magnetic order and superconductivity. Crystals of the spherical molecular C(60)(3-) anion support both superconductivity and magnetism but can consist of fundamentally distinct three-dimensional arrangements of the anions. Superconductivity in the A(3)C(60) (A = alkali metal) fullerides has been exclusively associated with face-centred cubic (f.c.c.) packing of C(60)(3-) (refs 2, 3), but recently the most expanded (and thus having the highest superconducting transition temperature, T(c); ref. 4) composition Cs(3)C(60) has been isolated as a body-centred cubic (b.c.c.) packing, which supports both superconductivity and magnetic order. Here we isolate the f.c.c. polymorph of Cs(3)C(60) to show how the spatial arrangement of the electronically active units controls the competing superconducting and magnetic electronic ground states. Unlike all the other f.c.c. A(3)C(60) fullerides, f.c.c. Cs(3)C(60) is not a superconductor but a magnetic insulator at ambient pressure, and becomes superconducting under pressure. The magnetic ordering occurs at an order of magnitude lower temperature in the geometrically frustrated f.c.c. polymorph (Néel temperature T(N) = 2.2 K) than in the b.c.c.-based packing (T(N) = 46 K). The different lattice packings of C(60)(3-) change T(c) from 38 K in b.c.c. Cs(3)C(60) to 35 K in f.c.c. Cs(3)C(60) (the highest found in the f.c.c. A(3)C(60) family). The existence of two superconducting packings of the same electronically active unit reveals that T(c) scales universally in a structure-independent dome-like relationship with proximity to the Mott metal-insulator transition, which is governed by the role of electron correlations characteristic of high-temperature superconducting materials other than fullerides.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                10 May 2016
                2016
                : 7
                : 11555
                Affiliations
                [1 ]Complex Functional Materials Group, School of Chemistry, University of Bristol , Bristol BS8 1TS, UK
                [2 ]School of Physics, HH Wills Physics Laboratory, Tyndall Avenue , Bristol BS8 1TL, UK
                [3 ]High Field Magnet Laboratory (HFML-EMFL), Radboud University , Toernooiveld 7, 6525 ED Nijmegen, The Netherlands
                [4 ]Bristol Centre for Functional Nanomaterials, HH Wills Physics Laboratory , Tyndall Avenue, Bristol BS8 1TL, UK
                [5 ]Department of Physics, University of Bath, Claverton Down , Bath BA2 7AY, UK
                [6 ]Dipartimento di Ingegneria Enzo Ferrari, Universita' di Modena e Reggio Emilia , Via Vivarelli 10, 41125 Modena, Italy
                [7 ]Department of Chemistry, University of Bath, Claverton Down , Bath BA2 7AY, UK
                Author notes
                Article
                ncomms11555
                10.1038/ncomms11555
                4866376
                27161600
                34e81d40-64f2-4091-9ea8-2ae07499c2cd
                Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 01 December 2015
                : 07 April 2016
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