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Controlling anisotropic properties by manipulating the orientation of chiral small molecules

Nature Chemistry volume 14, pages 1383–1389 (2022)Cite this article

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Abstract

Chiral π-conjugated molecules bring new functionality to technological applications and represent an exciting, rapidly expanding area of research. Their functional properties, such as the absorption and emission of circularly polarized light or the transport of spin-polarized electrons, are highly anisotropic. As a result, the orientation of chiral molecules critically determines the functionality and efficiency of chiral devices. Here we present a strategy to control the orientation of a small chiral molecule (2,2′-dicyano[6]helicene) by the use of organic and inorganic templating layers. Such templating layers can either force 2,2′-dicyano[6]helicene to adopt a face-on orientation and self-assemble into upright supramolecular columns oriented with their helical axis perpendicular to the substrate, or an edge-on orientation with parallel-lying supramolecular columns. Through such control, we show that low- and high-energy chiroptical responses can be independently ‘turned on’ or ‘turned off’. The templating methodologies described here provide a simple way to engineer orientational control and, by association, anisotropic functional properties of chiral molecular systems for a range of emerging technologies.

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Fig. 1: A schematic describing the motivation for this work and a description of the materials used.
Fig. 2: Spectroscopic and morphological characterization of untemplated and templated CN6H thin films.
Fig. 3: Experimental and simulated 2D GIWAXS diffraction patterns of untemplated and templated CN6H thin films.
Fig. 4: The molecular origins of optical transitions in CN6H and chiroptical spectra acquired for untemplated and templated thin films.

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Data availability

Source data are provided with this paper. Data for the main and extended figures are available at https://doi.org/10.14469/hpc/10763.

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Acknowledgements

We thank the EPSRC for funding (EP/R00188X/1, EP/F039948/1 and EP/L016702/1). We also thank the company Xenocs for their help and ongoing support with the X-ray scattering instrument based at The University of Sheffield and we thank the EPSRC for funding the purchase of this instrument. We thank the Department of Materials at Imperial College London for supporting an Imperial College Research Fellowship (JW) and PhD (DK). We thank A. Maho for his assistance with the SEM. We also thank G. Siligardi of the Diamond B23 beamline for his assistance on beamtimes SM29151. This project was supported by access to instrumentation at the Centre for Rapid Online Analysis of Reactions (ROAR) at Imperial College London (EPSRC, EP/R008825/1 and EP/V029037/1). J.N. thanks the European Research Council for the award of an Advanced Grant under Horizon 2020 (action no. 742708), and the Royal Society for a Research Professorship. K.E.J. thanks the Royal Society for a University Research Fellowship and an Enhancement Award and the European Research Council for the award of a Starting Grant under FP7 (CoMMaD, ERC Grant no. 758370). T.M. thanks CREST, JST, Japan for a grant (no. JPMJCR2001). E.R.J. and L.M.L. thank the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Walter C. Sumner Foundation for financial support. We also thank Compute Canada for computational resources.

Author information

Author notes

  1. These authors contributed equally: Francesco Salerno, Rachel C. Kilbride.

Authors and Affiliations

  1. Department of Materials and London Centre for Nanotechnology, Imperial College London, London, UK

    Jessica Wade, Dong Kuk Kim & Sandrine Heutz

  2. Centre for Processable Electronics, Imperial College London, London, UK

    Jessica Wade, Francesco Salerno, Dong Kuk Kim, Jenny Nelson, Kim E. Jelfs, Sandrine Heutz & Matthew J. Fuchter

  3. Department of Chemistry and Molecular Sciences Research Hub, Imperial College London, London, UK

    Francesco Salerno, Julia A. Schmidt, Emma H. Wolpert, Kim E. Jelfs & Matthew J. Fuchter

  4. Department of Physics and Astronomy, The University of Sheffield, Sheffield, UK

    Rachel C. Kilbride

  5. Department of Physics, Clarendon Laboratory, University of Oxford, Oxford, UK

    Joel A. Smith

  6. Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada

    Luc M. LeBlanc, Adebayo A. Adeleke & Erin R. Johnson

  7. Department of Physics, Imperial College London, London, UK

    Jenny Nelson

  8. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Japan

    Tadashi Mori

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Contributions

J.W., M.J.F. and S.H. developed the concepts behind this research. F.S. synthesized the chiral small molecule (CN6H). J.W. and D.K.K. fabricated the samples and also performed the spectroscopic experiments, 1D XRD and AFM. R.C.K. and J.A. Smith performed the GIWAXS and X-ray simulations. J.A. Schmidt, K.J., J.N., E.R.J., L.M.L., E.W. and A.A.A. performed the quantum chemical calculations and CSP. F.S. and T.M. performed the time-dependent density functional theory and CD simulations. J.W., M.J.F., S.H., K.J. and J.N. supervised the study and obtained funding. All the authors contributed to the writing of the manuscript.

Corresponding authors

Correspondence to Jessica Wade or Matthew J. Fuchter.

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The authors declare the following competing financial interest(s): M.F. is an inventor on a patent concerning chiral blend materials (WO2014016611).

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Extended data

Extended Data Fig. 1 Solution-state absorbance and photoluminescence spectra.

Absorption and photoluminescence spectra of CN6H in acetonitrile (2·10 − 5 M). The excitation wavelength was 325 nm.

Source data

Extended Data Fig. 2 UV-Visible absorption and circular dichroism of neat templating layers.

(a)UV-Vis and Circular Dichroism of the templating layers (PTCDA: 20 nm, CuI: 100 nm). (b)UV-Vis of CN6H [M] thin films subtracting the absorbance of the templating layers.

Source data

Extended Data Fig. 3 UV-Visible absorption and photoluminescence spectra of CN6H thin films.

(a)UV-visible absorption spectra of CN6H thin films (thickness: 78 nm) on a non-interacting substrate (quartz, black line), 20 nm PTCDA (red) and 100 nm CuI (111) (blue line). (b) Photoluminescence spectra of CN6H thin films (thickness: 78 nm) on a non-interacting substrate (quartz, black line), 20 nm PTCDA (red) and 100 nm CuI (111) (blue line). The excitation wavelength was 325 nm.

Source data

Extended Data Fig. 4 XRD of CN6H [P] thin films.

X-Ray diffraction patterns of CN6H thin films (thickness: 78 nm) on a non-interacting substrate (quartz, black line), 20 nm PTCDA (red) and 100 nm CuI (111) (blue line).

Source data

Extended Data Fig. 5 Atomic force microscopy of CN6H thin films.

(a)Atomic force microscopy images of CuI-templated CN6H [M]. The scale bar is indicated and the z-scale is in nm. (b)Atomic force microscopy image of untemplated and templated CN6H [P]. The scale bar is 1 µm. We note that the topography of the neat templating layers has been reported elsewhere, with surfaces of the 100 nm CuI thin films featuring large, pinhole-free smooth grains 30. The neat PTCDA layers are too sticky to successfully image. These types of strong interactions contribute to the broad distribution of supramolecular columns orientations illustrated in Fig. 3.

Source data

Extended Data Fig. 6 Planar and cross-sectional view scanning electron microscopy.

The dramatically different morphologies are also apparent in cross-sectional view SEM (a – c): in particular, the smooth surface of the flat-lying supramolecular columns of CuI-templated CN6H and uneven, rough surfaces of PTCDA-templated CN6H. Remarkably, PTCDA-templated CN6H appears to form molecular clusters in domains that extend throughout the entire film thickness, whilst there is some evidence of a layering in the platelet-packing on CuI. The ultra-smooth films of CuI-templated CN6H is responsible for the poor contrast in the planar view SEM.

Source data

Extended Data Fig. 7 CN6H [P] 2D GIWAXS Patterns and Simulations.

Experimental and simulated two-dimensional (2D) GIWAXS diffraction patterns of untemplated and templated CN6H [P]. In contrast to CN6H [M], the 1 0 0 reflection of untemplated CH6H [P], has a stronger out-of-plane intensity and the experimentally observed 2D GIWAXS pattern can be replicated by simulating a broad distribution with (1 0 0) planes parallel to the substrate. For PTCDA-templated CH6H [P], the scattering intensity is stronger compared to CN6H [M] but the 2D GIWAXS patterns of both enantiomers can be replicated by simulating a face-on arrangement of supramolecular columns with a reasonably broad distribution of crystallite orientations. CuI-templated CN6H [P] exhibits smaller Bragg spots compared to CN6H [M] but both enantiomers exhibit edge-on orientation and are simulated using the same uniaxial model. We attributed the small differences between CN6H [P] and [M] to experimental variations. Part (f) is repeated from Fig. 3f.

Source data

Extended Data Fig. 8 Comparison of powder XRD simulations and Q-dependent 1D profiles.

Azimuthally integrated Q-dependent 1D intensity profiles of untemplated and templated CN6H [M] and CN6H [P], integrated in the range 0.2 Å-1 ≤ Q ≤ 2.2 Å−1 through various χ angles; out-of-plane (in the Qz direction, χ = 0°±20°) and in-plane (which includes all other angles 20° ≤ χ ≤ 90°). The simulated powder XRD from Supplementary Fig. 2 is overlayed and the highest intensity reflections are labelled with the corresponding Miller indices. We attribute the small differences between CN6H [M] and CN6H [P] to experimental variations.

Source data

Extended Data Fig. 9 Proposed mechanism for PTCDA templating.

Theoretical molecular electrostatic potential surfaces (a) CN6H and (b) PTCDA calculated using DFT using the B3LYP hybrid functional with the 6-311G(d,p) basis set. The red areas represent electron rich regions of the molecule, whilst the blue areas represent electron poor regions. (c) a cartoon depicting the π-π interactions of flat-lying PTCDA and CN6H.

Source data

Extended Data Fig. 10 Proposed mechanism for CuI templating.

(a) Side and top-view of the crystal packing of CuI along the (111) plane, showing the relative positions of the iodine and copper atoms. The surface primarily consists of iodine atoms. (b) and (c) Theoretical molecular electrostatic potential surfaces of CN6H and a cartoon of the electrostatic interactions that force the edge-on configuration of CN6H on CuI.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–11, Discussions 1–5 and Tables 1 and 2.

Source data

Source Data Fig. 2

AFM images, UV-Vis/XRD data, Lattice plane diagrams.

Source Data Fig. 3

Experimental and simulated two-dimensional (2D) GIWAXS diffraction patterns of untemplated and templated CN6H [M].

Source Data Fig. 4

Illustrator file of graphic, CD data, molecular structure.

Source Data Extended Data Fig. 1

Unprocessed absorption and fluorescence data.

Source Data Extended Data Fig. 2

Unprocessed absorption and circular dichroism spectra.

Source Data Extended Data Fig. 3

Unprocessed absorption and photoluminescence data.

Source Data Extended Data Fig. 4

Unprocessed XRD data.

Source Data Extended Data Fig. 5

Levelled/background subtracted AFM images.

Source Data Extended Data Fig. 6

Unprocessed cross-sectional and planar SEM images.

Source Data Extended Data Fig. 7

Experimental and simulated two-dimensional (2D) GIWAXS diffraction patterns of untemplated and templated CN6H [P].

Source Data Extended Data Fig. 8

Azimuthally integrated Q-dependent 1D intensity profiles of untemplated and templated CN6H [M] and CN6H [P], integrated in the range 0.2 Å-1 ≤ Q ≤ 2.2 Å-1 through various χ angles; out-of-plane (in the Qz direction, χ = 0°±20°) and in-plane (which includes all other angles 20° ≤ χ ≤ 90°).

Source Data Extended Data Fig. 9

Molecular electrostatic potential surfaces calculated using DFT using the B3LYP hybrid functional at the 6-311 G(d,p) level of theory.

Source Data Extended Data Fig. 10

Crystal packing of CuI along the (111) plane, molecular electrostatic potential surfaces of CN6H.

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Wade, J., Salerno, F., Kilbride, R.C. et al. Controlling anisotropic properties by manipulating the orientation of chiral small molecules. Nat. Chem. 14, 1383–1389 (2022). https://doi.org/10.1038/s41557-022-01044-6

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