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Internal Dynamics in Helical Molecules Studied by X-Ray Diffraction, NMR Spectroscopy and DFT Calculations

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Internal Dynamics in Helical Molecules Studied by X-Ray Diffraction, NMR Spectroscopy and DFT Calculations PCCP View Article Online PAPER View Journal | View Issue Internal dynamics in helical molecules studied by X-ray diffraction, NMR spectroscopy and Cite this: Phys. Chem. Chem. Phys., 2017, 19, 2900 DFT calculations† a b b c b Martin Dracˇ´ınsky´,* Jan Storch, Vladimı´rCı´rkva, Ivana Cı´sarˇova´ and Jan Sy´kora* The conformational behaviour of a prototype helical molecule, [6]helicene, and its derivatives was studied in solution and the solid state. Available crystal structures of [6]helicene revealed surprisingly large flexibility of this molecule and variable-temperature NMR experiments provided unusual temperature dependence of Received 4th November 2016, chemical shifts of hydrogen, carbon and fluorine atoms in the peripheral aromatic rings of [6]helicene and Accepted 25th December 2016 tetrafluoro[6]helicene. These chemical shift changes were interpreted as a consequence of the helicene DOI: 10.1039/c6cp07552e ‘pitch’ opening with elevated temperature, and the experimental data were corroborated by DFT calculations of the chemical shift dependence on the helicene conformation and by variable-temperature DFT molecular www.rsc.org/pccp dynamics simulations. Creative Commons Attribution 3.0 Unported Licence. Introduction polymers.20 Undoubtedly, these valuable properties are closely connected with the overall structure of the molecule. Helicenes are polycyclic aromatic compounds consisting of Unsubstituted helicenes usually crystallise in non- ortho-fused benzene rings with nonplanar helical topology, centrosymmetric space groups (P21, P212121) despite the fact resulting from the steric repulsive interaction between peripheral that the helicenes are racemic.21–25 This phenomenon involves aromatic rings.1 This helical character makes helicenes chiral even so-called ‘lamellar twinning’, where the layers of individual This article is licensed under a though they have no centre of chirality. Furthermore, helicene enantiomers alternate within a single crystal, forming homo- molecules also possess a twofold axis of symmetry perpendicular chiral domains.26 Some of the derivatives have a tendency towards to the axis of helicity. co-facial stacking in bulk state forming macroscopic fibres Open Access Article. Published on 03 January 2017. Downloaded 9/27/2021 7:17:46 PM. The highly delocalised large p-electron system of fully aromatic consisting of columnar aggregates. Similar self-assembly motifs helicenes along with the previously mentioned inherent chirality can be also found in Langmuir–Blodgett films prepared by dip provide them with unique optical and electronic properties. The or spin coating.27,28 Due to the perpendicular arrangement of helicenes achieve e.g. exceptionally high values of specific rotation the aromatic rings with respect to the surface, the deposited (thousands of degrees per mole).2 They also provide strong films are usually anisotropic.29 circular dichroism,3 electroluminescence,4,5 circularly polarised Starting from [6]helicene, the twisted molecule of helicenes luminescence,6,7 and non-linear optical properties.8–11 Furthermore, is highly constrained due to the steric hindrance of the peripheral helicenes exhibit semi-conductive behaviour.12,13 All of these proper- rings, which gives the impression of rigidity. However, a comparison ties predetermine their utilisation in a wide range of applications in of accessible crystal structures of [6]helicene reveals surprising organic electronic devices.14–16 The chirality of helicenes has also flexibility within a certain range of the molecular conformation. been utilised in the chiral discotic liquid-crystalline materials, or On the one hand, there is a crystal structure of a charge-transfer these molecules have served as ligands in asymmetric catalysis.17–19 complex of [6]helicene with trimesic acid, which has provided In addition, they can be used as building blocks in functional the most compressed conformation of the [6]helicene molecule with the distance between C2 and C20 atoms of the peripheral 30 a Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, rings of 3.94 Å (Fig. 1). On the other hand, the helicene Flemingovo 2, 16610 Prague, Czech Republic. E-mail: [email protected] conformation can be stretched by the insertion of another b Institute of Chemical Process Fundamentals, Czech Academy of Sciences, molecule or atom into the helicene pitch, such as in the crystal Rozvojova´ 135, 16502 Prague, Czech Republic. E-mail: [email protected] structure of plain [6]helicene (the C2–C20 distance of 4.58 Å in c Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague, the original structure from 1973),21 which consists of pairs of Czech Republic † Electronic supplementary information (ESI) available: Additional experimental interlocked helicene molecules, or a [6]helicene complex with 1 and computational data. CCDC 1514731–1514735. For ESI and crystallographic silver salts, where the silver ion is bound by Z bond to C2 and 31 data in CIF or other electronic format see DOI: 10.1039/c6cp07552e C20 atoms, giving the C2–C20 distance of 4.61 Å. The adopted 2900 | Phys. Chem. Chem. Phys., 2017, 19, 2900--2907 This journal is © the Owner Societies 2017 View Article Online Paper PCCP Fig. 1 The crystal structure of (a) [6]helicene, (b) [6]helicene-trimesic acid (benzene-1,3,5-tricarboxylic acid), (c) Ag–[6]helicene complex, (d) [6]helicene–perfluorobenzene complex and (e) tetrafluoro[6]helicene. Complete atom numbering is shown in the ESI.† conformation is a consequence of intra- and intermolecular T = 150 K, crystal dimensions of 0.1 Â 0.15 Â 0.2 mm. The interactions in the crystal lattice and induces deformations of structure converged to the final R = 0.0345 and Rw = 0.0797 individual aromatic rings. using 1682 independent reflections for 299 parameters This paper presents an original study of internal dynamics in (ymax = 27.501). The obtained structure is almost identical to that [6]helicenes both in solution and the solid state with special obtained by De Clercq.21 Variable-temperature X-ray structure attention to the helicene pitch opening. It analyses the temperature analysis was performed at 100, 150 and 300 K, CCDC 1514732 dependence of the structural parameters determined by X-ray (100 K), 1514734 (150 K) and 1514735 (300 K). The hydrogen diffraction and of NMR chemical shifts. The experimental results atoms of the crystal structure measured at 300 K were located are subsequently confronted with DFT calculations and molecular from the expected geometry and were not refined. The variable- Creative Commons Attribution 3.0 Unported Licence. dynamics simulations. It is shown that a combination of experi- temperature calculation results are summarised in the ESI† mental and theoretical approaches allows a precise description of (Table S1). the conformational behaviour of helicenes. X-ray of the [6]helicene–perfluorobenzene complex À1 Methods C26H16.CF6, M =514.47gmol , monoclinic system, space group C2/c, a = 7.4459(4), b = 17.9293(9), c = 17.1981(10) Å, b = 98.529(2), 3 À3 À1 [6]Helicene (puriss., Z99%) was purchased from Lach-ner, Czech Z =4,V = 2270.6(2) Å , Dc =1.51gcm , m(MoKa)=1.21mm , Republic. Single crystals of [6]helicene suitable for X-ray structure T = 150 K, crystal dimensions of 0.20 Â 0.40 Â 0.61 mm. The This article is licensed under a analysis were obtained by crystallisation from chloroform. The structure converged to the final R =0.0404andRw = 0.0926 using charge-transfer complex of [6]helicene with perfluorobenzene was 2301 independent reflections for 205 parameters (ymax = 27.521), obtained by crystallisation from chloroform–perfluorobenzene CCDC 1514731. mixture. 1,2,3,4-Tetrafluoro[6]helicene was prepared by intra- Open Access Article. Published on 03 January 2017. Downloaded 9/27/2021 7:17:46 PM. molecular photocyclisation of tetrafluoro-2,7-distyrylnaphthalene X-ray of tetrafluoro[6]helicene using the Mallory-type reaction.32 The detailed synthesis will be À1 C26H12F4, M = 400.36 g mol , monoclinic system, space group published separately. Single crystals of 1,2,3,4-tetrafluoro[6]helicene P21/n, a = 7.5783(6), b = 20.3575(16), c = 11.4292(8) Å, were obtained by crystallisation from chloroform. 3 À3 b = 101.178(3), Z =4,V = 1729.8(2) Å , Dc = 1.54 g cm , À1 Diffraction data were collected at 150 K on a Nonius Kappa m(MoKa) = 1.15 mm , T = 150 K, crystal dimensions of CCD diffractometer (Enraf-Nonius) with graphite-monochromated 0.16 Â 0.39 Â 0.67 mm. The structure converged to the final Mo-Ka radiation. A Cryostream Cooler (Oxford Cryosystem) was R = 0.0410 and Rw = 0.0869 using 3750 independent reflections used for low-temperature measurements. The structures were for 319 parameters (ymax = 27.431), CCDC 1514733. 33 34 solved by direct methods (SIR92, SHELXL97 )andrefinedby NMR spectra were measured at room temperature on a 2 35 full-matrix least-squares on F values (CRYSTALS ). All heavy atoms Bruker Avance III spectrometer operating at 600.1 MHz for were refined anisotropically. Hydrogen atoms were localised from 1 13 H and at 150.9 MHz for C in DMSO-d6 and aceton-d6. the expected geometry and difference electron density maps and A combination of 1D and 2D experiments (COSY, HSQC, HMBC) 36 were refined isotropically. PARST97 was used for the calculation was used for the assignment of all 1Hand13Cresonances. 37 of ring-puckering parameters. The details of atom numbering Variable-temperature NMR experiments were performed on and the complete list of puckering parameters are listed in the a Bruker Avance II spectrometer operating at 499.9 MHz for 38 ESI.† ORTEP-3 was used for structure presentation. 1H, 470.3 MHz for 19F and at 125.7 MHz for 13C. Temperature was calibrated with methanol and ethyleneglycol; a 200–400 K X-ray of [6]helicene temperature range with 50 K steps was used for the experiments.
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