Recently, a large family of at least 14 discotic liquid crystals was discovered that are exceptions to the conventional paradigm that discotic mesogens tend to feature long, flexible tails on their periphery. To understand why these materials are liquid crystals, as well as the structural determinants of discotic phase behavior, we studied a group of closely related small tail-free disk-like molecules, including both mesogenic and non-mesogenic compounds differing only in the position of a single fluorine substituent. The rigidity and structural simplicity of these molecules make them well suited to for study by large, fully all-atom simulations. Using a combination of static and dynamic metrics, we were able to identify several key features of the columnar mesophase and, thereby, conclusively identify a columnar liquid crystalline mesophase present in a subset of our systems. Our simulations feature molecules hopping between columns in the columnar mesophase and distinctive molecular rotations in 60° steps about the columnar axis. The ability to create and characterize columnar mesophases in silico provides a potent tool for untangling the structural determinants of liquid crystalline behavior in these and other tail-free discotic liquid crystals.
REFERENCES
1.
S.
Chandrasekhar
, “Columnar, discotic nematic and lamellar liquid crystals: Their structures and physical properties
,” in Handbook of Liquid Crystals Set
(Wiley
, 1998
), Chap. VIII, p. 749
.2.
T.
Wöhrle
, I.
Wurzbach
, J.
Kirres
, A.
Kostidou
, N.
Kapernaum
, J.
Litterscheidt
, J. C.
Haenle
, P.
Staffeld
, A.
Baro
, F.
Giesselmann
, and S.
Laschat
, “Discotic liquid crystals
,” Chem. Rev.
116
, 1139
(2016
).3.
S.
Laschat
, A.
Baro
, N.
Steinke
, F.
Giesselmann
, C.
Hägele
, G.
Scalia
, R.
Judele
, E.
Kapatsina
, S.
Sauer
, A.
Schreivogel
, and M.
Tosoni
, “Discotic liquid crystals: From tailor-made synthesis to plastic electronics
,” Angew. Chem., Int. Ed.
46
, 4832
(2007
).4.
S.
Sergeyev
, W.
Pisula
, and Y. H.
Geerts
, “Discotic liquid crystals: A new generation of organic semiconductors
,” Chem. Soc. Rev.
36
, 1902
(2007
).5.
R.
Termine
and A.
Golemme
, “Charge mobility in discotic liquid crystals
,” Int. J. Mol. Sci.
22
, 877
(2021
).6.
M.
Sorai
and K.
Saito
, “Alkyl chains acting as entropy reservoir in liquid crystalline materials
,” Chem. Rec.
3
, 29
(2003
).7.
S.
Basurto
, S.
García
, A. G.
Neo
, T.
Torroba
, C. F.
Marcos
, D.
Miguel
, J.
Barberá
, M. B.
Ros
, and M. R.
de la Fuente
, “Indene and pseudoazulene discotic liquid crystals: A synthetic and structural study
,” Chem. - Eur. J.
11
, 5362
(2005
).8.
R. J.
Twieg
, B.
Ellman
, Z.
Li
, M.
Powers
et al., “Fluorinated tail-free triphenylene discotic liquid crystals
” (unpublished) (2022
).9.
F. M.
Van Der Kooij
, K.
Kassapidou
, and H. N. W.
Lekkerkerker
, “Liquid crystal phase transitions in suspensions of polydisperse plate-like particles
,” Nature
406
, 868
(2000
).10.
J. A. C.
Veerman
and D.
Frenkel
, “Phase behavior of disklike hard-core mesogens
,” Phys. Rev. A
45
, 5632
(1992
).11.
H.
Azzouz
, J. M.
Caillol
, D.
Levesque
, and J. J.
Weis
, “Phase behavior of parallel cut spheres. Monte Carlo and integral equation results
,” J. Chem. Phys.
96
, 4551
(1992
).12.
M.
Marechal
, A.
Cuetos
, B.
Martínez-Haya
, and M.
Dijkstra
, “Phase behavior of hard colloidal platelets using free energy calculations
,” J. Chem. Phys.
134
, 094501
(2011
).13.
A.
Cuetos
, M.
Dennison
, A.
Masters
, and A.
Patti
, “Phase behaviour of hard board-like particles
,” Soft Matter
13
, 4720
(2017
).14.
A.
Patti
, S.
Belli
, R.
van Roij
, and M.
Dijkstra
, “Relaxation dynamics in the columnar liquid crystal phase of hard platelets
,” Soft Matter
7
, 3533
(2011
).15.
A. P. J.
Emerson
, G. R.
Luckhurst
, and S. G.
Whatling
, “Computer simulation studies of anisotropic systems
,” Mol. Phys.
82
, 113
(1994
).16.
M. A.
Bates
and G. R.
Luckhurst
, “Computer simulation studies of anisotropic systems. XXVI. Monte Carlo investigations of a Gay–Berne discotic at constant pressure
,” J. Chem. Phys.
104
, 6696
(1996
).17.
O.
Cienega-Cacerez
, J. A.
Moreno-Razo
, E.
Díaz-Herrera
, and E. J.
Sambriski
, “Phase equilibria fluid structure and diffusivity of a discotic liquid crystal
,” Soft Matter
10
, 3171
–3182
(2014
).18.
R.
Berardi
, S.
Orlandi
, and C.
Zannoni
, “Columnar and interdigitated structures from apolar discotic mesogens with radial dipoles: A Monte Carlo study
,” Liq. Cryst.
32
, 1427
–1436
(2005
).19.
R.
Busselez
, C. V.
Cerclier
, M.
Ndao
, A.
Ghoufi
, R.
Lefort
, and D.
Morineau
, “Discotic columnar liquid crystal studied in the bulk and nanoconfined states by molecular dynamics simulation
,” J. Chem. Phys.
141
, 134902
(2014
).20.
G.
Cinacchi
, R.
Colle
, and A.
Tani
, “Atomistic molecular dynamics simulation of hexakis(pentyloxy)triphenylene: Structure and translational dynamics of its columnar state
,” J. Phys. Chem. B
108
, 7969
(2004
).21.
D.
Andrienko
, V.
Marcon
, and K.
Kremer
, “Atomistic simulation of structure and dynamics of columnar phases of hexabenzocoronene derivatives
,” J. Chem. Phys.
125
, 124902
(2006
).22.
P. L.
Cristinziano
and F.
Lelj
, “Atomistic simulation of discotic liquid crystals: Transition from isotropic to columnar phase example
,” J. Chem. Phys.
127
, 134506
(2007
).23.
L.
Muccioli
, R.
Berardi
, S.
Orlandi
, M.
Ricci
, and C.
Zannoni
, “Molecular properties and stacking of 1-substituted hexaalkoxy triphenylenes
,” Theor. Chem. Acc.
117
, 1085
(2007
).24.
S.
Orlandi
, L.
Muccioli
, M.
Ricci
, R.
Berardi
, and C.
Zannoni
, “Core charge distribution and self assembly of columnar phases: The case of triphenylenes and azatriphenylenes
,” Chem. Cent. J.
1
, 15
(2007
).25.
V.
Marcon
, T.
Vehoff
, J.
Kirkpatrick
, C.
Jeong
, D. Y.
Yoon
, K.
Kremer
, and D.
Andrienko
, “Columnar mesophases of hexabenzocoronene derivatives. I. Phase transitions
,” J. Chem. Phys.
129
, 094505
(2008
).26.
Y.
Olivier
, L.
Muccioli
, V.
Lemaur
, Y. H.
Geerts
, C.
Zannoni
, and J.
Cornil
, “Theoretical characterization of the structural and hole transport dynamics in liquid-crystalline phthalocyanine stacks
,” J. Phys. Chem. B
113
, 14102
–14111
(2009
).27.
L. A.
Haverkate
, M.
Zbiri
, M. R.
Johnson
, B.
Deme
, F. M.
Mulder
, and G. J.
Kearley
, “Conformation, defects, and dynamics of a discotic liquid crystal and their influence on charge transport
,” J. Phys. Chem. B
115
, 13809
(2011
).28.
F.
Camerel
, F.
Barrière
, and O.
Jeannin
, “Simulation of SAXS patterns of hexa-n-alkoxy-2,3,6,7,10,11-triphenylene mesophase
,” Liq. Cryst.
45
, 698
(2018
).29.
M.
Valiev
, E. J.
Bylaska
, N.
Govind
, K.
Kowalski
, T. P.
Straatsma
, H. J. J.
van Dam
, D.
Wang
, J.
Nieplocha
, E.
Aprà
, T. L.
Windus
, and W. A.
de Jong
, “NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
,” Comput. Phys. Commun.
181
, 1477
(2010
).30.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
, G. E.
Scuseria
et al., Gaussian 16 Revision C.01, Gaussian, Inc.
, Wallingford, CT
, 2016
.31.
U. C.
Singh
and P. A.
Kollman
, “An approach to computing electrostatic charges for molecules
,” J. Comput. Chem.
5
, 129
(1984
).32.
W. L.
Jorgensen
, “OPLS all-atom parameters for organic molecules, ions, peptides and nucleic acids, July 2008
,” as provided by W. L. Jorgensen, Yale University during June 2009. Theseparameters are taken from those distributed with BOSS Version 4.8.33.
C.
Gray
and K.
Gubbins
, Theory of Molecular Fluids. Volume 1: Fundamentals
(Clarendon Press
, 1984
).34.
CRC Handbook of Chemistry and Physics
, 102nd ed., edited by J.
Rumble
(CRC Press
, London, England
, 2021
).35.
J. A.
Rackers
, Z.
Wang
, C.
Lu
, M. L.
Laury
, L.
Lagardère
, M. J.
Schnieders
, J.-P.
Piquemal
, P.
Ren
, and J. W.
Ponder
, “Tinker 8: Software tools for molecular design
,” J. Chem. Theory Comput.
14
, 5273
(2018
).36.
G.
Bussi
and M.
Parrinello
, “Stochastic thermostats: Comparison of local and global schemes
,” Comput. Phys. Commun.
179
, 26
(2008
).37.
H. J. C.
Berendsen
, J. P. M.
Postma
, W. F.
Van Gunsteren
, A.
Dinola
, and J. R.
Haak
, “Molecular dynamics with coupling to an external bath
,” J. Chem. Phys.
81
, 3684
(1984
).38.
S.
Toxvaerd
and J. C.
Dyre
, “Communication: Shifted forces in molecular dynamics
,” J. Chem. Phys.
134
, 081102
(2011
).39.
D.
Wolf
, P.
Keblinski
, S. R.
Phillpot
, and J.
Eggebrecht
, “Exact method for the simulation of Coulombic systems by spherically truncated, pairwise r−1 summation
,” J. Chem. Phys.
110
, 8254
(1999
).40.
P. J.
Steinbach
and B. R.
Brooks
, “New spherical-cutoff methods for long-range forces in macromolecular simulation
,” J. Comput. Chem.
15
, 667
(1994
).41.
M.
Lamichhane
, K. E.
Newman
, and J. D.
Gezelter
, “Real space electrostatics for multipoles. II. comparisons with the Ewald sum
,” J. Chem. Phys.
141
, 134110
(2014
).42.
M. P.
Allen
and D. J.
Tildesley
, Computer Simulation of Liquids
(Oxford University Press
, 2017
).43.
J.
Vieillard-Baron
, “The equation of state of a system of hard spherocylinders
,” Mol. Phys.
28
, 809
(1974
).44.
S.
Khodadadi
and A. P.
Sokolov
, “Protein dynamics: From rattling in a cage to structural relaxation
,” Soft Matter
11
, 4984
(2015
).45.
R.
Pastore
, A.
Coniglio
, and M.
Pica Ciamarra
, “From cage-jump motion to macroscopic diffusion in supercooled liquids
,” Soft Matter
10
, 5724
(2014
).46.
C. H.
Rycroft
, “VORO++: A three-dimensional Voronoi cell library in C++
,” Chaos
19
, 041111
(2009
).47.
W.
Mickel
, S. C.
Kapfer
, G. E.
Schröder-Turk
, and K.
Mecke
, “Shortcomings of the bond orientational order parameters for the analysis of disordered particulate matter
,” J. Chem. Phys.
138
, 044501
(2013
).48.
W.
Shen
, J.
Antonaglia
, J. A.
Anderson
, M.
Engel
, G.
Van Anders
, and S. C.
Glotzer
, “Symmetries in hard polygon systems determine plastic colloidal crystal mesophases in two dimensions
,” Soft Matter
15
, 2571
(2019
).49.
M. P.
Lettinga
and E.
Grelet
, “Self-diffusion of rodlike viruses through smectic layers
,” Phys. Rev. Lett.
99
, 197802
(2007
).50.
G. S.
Kottas
, L. I.
Clarke
, D.
Horinek
, and J.
Michl
, “Artificial molecular rotors
,” Chem. Rev.
105
, 1281
(2005
).51.
J.
Leisen
, M.
Werth
, C.
Boeffel
, and H. W.
Spiess
, “Molecular dynamics at the glass transition: One dimensional and two dimensional nuclear magnetic resonance studies of a glass‐forming discotic liquid crystal
,” J. Chem. Phys.
97
, 3749
(1992
).52.
I.
Fischbach
, T.
Pakula
, P.
Minkin
, A.
Fechtenkötter
, K.
Müllen
, H. W.
Spiess
, and K.
Saalwächter
, “Structure and dynamics in columnar discotic materials: A combined X-ray and solid-state NMR study of hexabenzocoronene derivatives
,” J. Phys. Chem. B
106
, 6408
(2002
).53.
F.
Vaca Chávez
, P. J.
Sebastião
, Y.
Miyake
, H.
Monobe
, and Y.
Shimizu
, “Dynamics of discotic fluoroalkylated triphenylene molecules studied by proton NMR relaxometry
,” J. Phys. Chem. B
116
, 2339
(2012
).54.
J.
Timmermans
, “Plastic crystals: A historical review
,” J. Phys. Chem. Solids
18
, 1
–8
(1961
).55.
J. N.
Sherwood
, The Plastically Crystalline State: Orientationally Disordered Crystals
(Wiley
, 1979).56.
I. M.
Sokolov
, “Models of anomalous diffusion in crowded environments
,” Soft Matter
8
, 9043
(2012
).57.
P.
Polanowski
and A.
Sikorski
, “Molecular transport in systems containing binding obstacles
,” Soft Matter
15
, 10045
(2019
).58.
P.
Hopkins
, A.
Fortini
, A. J.
Archer
, and M.
Schmidt
, “The van Hove distribution function for Brownian hard spheres: Dynamical test particle theory and computer simulations for bulk dynamics
,” J. Chem. Phys.
133
, 224505
(2010
).59.
L.
Van Hove
, “Correlations in space and time and Born approximation scattering in systems of interacting particles
,” Phys. Rev.
95
, 249
(1954
).60.
A.
Cuetos
, N.
Morillo
, and A.
Patti
, “Fickian yet non-Gaussian diffusion is not ubiquitous in soft matter
,” Phys. Rev. E
98
, 042129
(2018
).61.
S.
Belli
, A.
Patti
, R.
van Roij
, and M.
Dijkstra
, “Heterogeneous dynamics in columnar liquid crystals of parallel hard rods
,” J. Chem. Phys.
133
, 154514
(2010
).62.
N.
Boden
, R. J.
Bushby
, J.
Clements
, K.
Donovan
, B.
Movaghar
, and T.
Kreouzis
, “Charge dynamics and recombination kinetics in columnar discotic liquid crystals
,” Phys. Rev. B
58
, 3063
(1998
).63.
X.
Shen
, R. Y.
Dong
, N.
Boden
, R. J.
Bushby
, P. S.
Martin
, and A.
Wood
, “Orientational ordering and dynamics in the columnar phase of a discotic liquid crystal studied by deuteron NMR spectroscopy
,” J. Chem. Phys.
108
, 4324
(1998
).© 2022 Author(s). Published under an exclusive license by AIP Publishing.
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