Chapter 7
Supramolecular, Hierarchical,
and Energetical Interpretation
of Organic Crystals: Generation
of Supramolecular Chirality
in Assemblies of Achiral Molecules
Mikiji Miyata and Seiji Tsuzuki
Abstract Recent progress in personal computers and computational methods has
enabled us to practically perform quantitative evaluation of intermolecular interaction energies of organic molecules consisting of more than one hundred carbon atoms
using density functional theory (DFT) calculations with dispersion correction. The
calculations prompted us to make a systematic method for defining dimeric molecular assemblies in organic crystals. Based on Z-matrix involving dummy atoms,
we designed a rectangular triangle model where a molecule positions through three
kinds of rotations. This model clarified generation of position-dependent chirality
along an axis. Symmetry operations, such as translation, two-fold rotation, twofold helix, and so on, connect the identical triangles to generate position-dependent
supramolecular chirality of the assemblies. The intermolecular interaction energies
of the dimers evaluated by the supermolecule method depend on assemble modes of
the dimers, leading us to the interpretation for hierarchical structures in crystals as
well as generation of supramolecular chirality from achiral molecules in the crystals.
Keywords DFT calculations · Dispersion correction · Position-dependent
chirality · Supramolecular chirality · Intermolecular interaction energy ·
Hierarchical structures · Chiral crystallization
M. Miyata (B)
The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki
567-0047, Osaka, Japan
e-mail: miyata@mls.eng.osaka-u.ac.jp
S. Tsuzuki
Research Center for Computational Design of Advanced Functional Materials (CD-FMat),
National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono,
Tsukuba 305-8568, Ibaraki, Japan
e-mail: s.tsuzuki@aist.go.jp
© Springer Nature Singapore Pte Ltd. 2020
M. Sakamoto and H. Uekusa (eds.), Advances in Organic Crystal Chemistry,
https://doi.org/10.1007/978-981-15-5085-0_7
115
Supramolecular, Hierarchical,
and Energetical Interpretation
of Organic Crystals: Generation
of Supramolecular Chirality
in Assemblies of Achiral Molecules
Mikiji Miyata and Seiji Tsuzuki
Abstract Recent progress in personal computers and computational methods has
enabled us to practically perform quantitative evaluation of intermolecular interaction energies of organic molecules consisting of more than one hundred carbon atoms
using density functional theory (DFT) calculations with dispersion correction. The
calculations prompted us to make a systematic method for defining dimeric molecular assemblies in organic crystals. Based on Z-matrix involving dummy atoms,
we designed a rectangular triangle model where a molecule positions through three
kinds of rotations. This model clarified generation of position-dependent chirality
along an axis. Symmetry operations, such as translation, two-fold rotation, twofold helix, and so on, connect the identical triangles to generate position-dependent
supramolecular chirality of the assemblies. The intermolecular interaction energies
of the dimers evaluated by the supermolecule method depend on assemble modes of
the dimers, leading us to the interpretation for hierarchical structures in crystals as
well as generation of supramolecular chirality from achiral molecules in the crystals.
Keywords DFT calculations · Dispersion correction · Position-dependent
chirality · Supramolecular chirality · Intermolecular interaction energy ·
Hierarchical structures · Chiral crystallization
M. Miyata (B)
The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki
567-0047, Osaka, Japan
e-mail: miyata@mls.eng.osaka-u.ac.jp
S. Tsuzuki
Research Center for Computational Design of Advanced Functional Materials (CD-FMat),
National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono,
Tsukuba 305-8568, Ibaraki, Japan
e-mail: s.tsuzuki@aist.go.jp
© Springer Nature Singapore Pte Ltd. 2020
M. Sakamoto and H. Uekusa (eds.), Advances in Organic Crystal Chemistry,
https://doi.org/10.1007/978-981-15-5085-0_7
115