How does molecular self-assembly take place?

Since the discovery of the phenomenon of molecular self-assembly, the mechanism of this phenomenon has remained a mystery for a long time. Our laboratory has been working on this issue since 2014, focussing on coordination self-assemblies, and has developed a unique analysis method called QASAP (Quantitative Analysis of Self-Assembly Process). Then, the formation mechanism of self-assemblies such as capsules, cages, and rings was revealed (see bellow). Through our research on the self-assembly processes of coordination assemblies, it was found that many coordination self-assemblies proceed through various pathways, unlike ordinary chemical reactions. QASAP can be used to investigate various molecular self-assembly processes, not limited to coordination self-assemblies. The goal of this project is to elucidate the principles governing molecular self-assembly by revealing the formation mechanism of a variety types of molecular self-assemblies. Only our laboratory in the world is systematically investigating the formation mechanism of coordination self-assemblies, and we are currently using QASAP to collaborate with researchers around the world. We are looking forward to starting new collaborating works with researchers who have originally developed molecular self-assemblies. If you are interested in the self-assembly processes of your system, please contact with us.

104Kinetically controlled narcissistic self-sorting of Pd(ii)-linked self-assemblies from structurally similar tritopic ligand.  

T. Abe, S. Horiuchi, and S. Hiraoka*

Chem. Commun. 58, 10829–10832 (2022). [DOI: 10.1039/D2CC04496J]

103. Cyclization or bridging: which occurs faster is the key to the self-assembly mechanism of Pd6L3coordination prisms. 

X. Zhang, S. Takahashi, K. Aratsu, I. Kikuchi, H. Sato, and S. Hiraoka*

Phys. Chem. Chem. Phys. 24, 2997–3006 (2022). [DOI: 10.1039/D1CP04448F] ‡: These authors equally contributed to this research.

H. Sato
Kyoto University

102. Unexpected self-assembly pathway to a Pd(II) coordination square- based pyramid and its preferential formation beyond the Boltzmann distribution.

T, Tateishi, S. Takahashi, I. Kikuchi, K. Aratsu, H. Sato, and S. Hiraoka*

Inorg. Chem. 60, 16678–16685 (2021). [DOI: 10.1021/acs.inorgchem.1c02570]

H. Sato
Kyoto University

98. Coordination Self-assembly Processes Revealed by Collaboration of Experiment and Theory: Toward Kinetic Control of Molecular Self-assembly.

S. Hiraoka*, S. Takahashi, and H. Sato

Chem. Rec. 21, 443 – 459 (2021). [DOI: 10.1002/tcr.202000124] (selected as Front Cover)

H. Sato
Kyoto University

97. Towards Kinetic Control of Coordination Self-Assembly: A Case Study of a Pd3L6 Double-Walled Triangle to Predict the Outcomes by a Reaction Network Model. 

S. Takahashi,* T. Tateishi, Y. Sasaki, H. Sato, and S. Hiraoka*

Phys. Chem. Chem. Phys. 22, 26614 – 26626 (2020). [DOI: 10.1039/d0cp04623j]

H. Sato
Kyoto University

96. Navigated Self-assembly of a Pd2L4 Cage by Modulation of an Energy Landscape under Kinetic Control.

T. Tateishi, S. Takahashi, A. Okazawa, V. Martí-Centelles, J. Wang, T. Kojima, P. J. Lusby,* H. Sato, and S. Hiraoka*

J. Am. Chem. Soc. 141, 19669 – 19676 (2019). [DOI: 10.1021/jacs.9b07779]

P. J. Lusby University of Edinburgh, UK
H. Sato
Kyoto University

95. Bifurcation of Self-assembly Pathways to Sheet or Cage Controlled by Kinetic Template Effect

L. H. Foianesi-Takeshige, S. Takahashi, T. Tateishi, R. Sekine, A. Okazawa, W. Zhu, T. Kojima, K. Harano, E. Nakamura, H. Sato, and S. Hiraoka*

Commun. Chem. 2, 128 (2019). [DOI: 10.1038/s42004-019-0232-2] Press release [Link]

E. Nakamura
the University of Tokyo
K. Harano
the University of Tokyo
H. Sato
Kyoto University

91. Self-assembly Processes of Octahedron-shaped Pd6L4 Cages. 

S. Komine, S. Takahashi, T. Kojima, H. Sato, and S. Hiraoka*

J. Am. Chem. Soc. 141, 3178 – 3186 (2019). [DOI: 10.1021/jacs.8b12890]

H. Sato
Kyoto University

90. Self-assembly Process of a Pd4L8 Quadruply Interlocked Cage.

 T. Tateishi, Y. Yasutake, T. Kojima, S. Takahashi, and S. Hiraoka*

Commun. Chem. 2, 25 (2019). [DOI10.1038/s42004-019-0123-6

88. Self-assembly Processes of Pd6L12 Cages.

S. Komine, T. Tateishi, T. Kojima, H. Nakagawa, Y. Hayashi, S. Takahashi, and S. Hiraoka*

Dalton Trans. 48, 4139 – 4148 (2019). [DOI: 10.1039/C8DT04931A] selected as Inside Front Cover and Hot Paper

87. Self-assembly Processes of Pd(II)- and Pt(II)-linked Discrete Self-assemblies Revealed by QASAP.

S. Hiraoka*

Isr. J. Chem. 59, 151 – 165 (2019). [DOI: 10.1002/ijch.201800073](Invited Account)

86. A Stochastic Model Study on the Self-Assembly Process of a Pd2L4 Cage Consisting of Rigid Ditopic Ligands.

 S. Takahashi*, Y. Sasaki, S. Hiraoka*, and H. Sato*

Phys. Chem. Chem. Phys. 21, 6341 – 6347 (2019). [DOI: 10.1039/C8CP06102E]selected as Outside Back Cover

H. Sato
Kyoto University

85. A Kinetics Study of Ligand Substitution Reaction on Dinuclear Platinum Complexes: Stochastic Versus Deterministic Approach

T. Iioka, S. Takahashi, Y. Yoshida, Y. Matsumura, S. Hiraoka, and H. Sato*

J. Comput. Chem. 1, 279 – 285 (2019). [DOI: 10.1002/jcc.25588]

H. Sato
Kyoto University

84. Self-Assembly of a Pd4L8 Double-Walled Square Takes Place through Two Kinds of Metastable Species. 

S. Kai, T. Tateishi, T. Kojima, S. Takahashi, and S. Hiraoka*

Inorg. Chem. 57, 13083 – 13086 (2018). [DOI: 10.1021/acs.inorgchem.8b02470]

キラルセルフソーティング の機構:どのようにエナンチオマーの選別が起こるのか

立石 友紀・小島 達央・平岡 秀一

現代化学, 9月号(570), 64–68 (2018).

80. Two Dominant Self-assembly Pathways to a Pd3L6 Double-walled Triangle.

 T. Tateishi, S. Kai, Y. Sasaki, T. Kojima, S. Takahashi, and S. Hiraoka*

Chem. Commun54, 7758 – 5561 (2018). [DOI: 10.1039/C8CC02608D] selected as Back Cover

78. Energy-Landscape-Independent Kinetic Trap of Incomplete Cage in the Self-assembly of a Pd2L4 Cage.

M. Nakagawa, S. Kai, T. Kojima, and S. Hiraoka*

Chem. Eur. J. 24, 8804–8808 (2018). [DOI: 10.1002/chem.201801183] selected as Hot Paper and Inside Cover

74. How Does Chiral Self-sorting Take Place in the Formation of Homochiral Pd6L8 Capsules Consisting of Cyclotriveratrylene-based Chiral Tritopic Ligands?

S. Kai, T. Kojima, F. L. Thorp-Greenwood, M. J. Hardie, and S. Hiraoka*

Chem. Sci. 9, 4104 – 4108 (2018). [DOI: 10.1039/C8SC01062E]

M. J. Hardie
University of Leeds, UK

73. Unresolved Issues that Remain in Molecular Self-Assembly. 

S. Hiraoka*

Bull. Chem. Soc. Jpn. 91, 957–978 (2018). [DOI: 10.1246/bcsj.20180008] Commemorative Accounts: Self-Organization

71. Chiral Self-sorting Process in the Self-assembly of Homochiral Coordination Cages from Axially Chiral Ligands. 

T. Tateishi, T. Kojima, and S. Hiraoka*

Commun. Chem. 1, 20 (2018). [DOI: 10.1038/s42004-018-0020-4]. 

68. Flexibility of Components Alters the Self-assembly Pathway of Pd2L4 Coordination Cages.

S. Kai, S. P. Maddala, T. Kojima, S. Akagi, K. Harano, E. Nakamura, and S. Hiraoka*

Dalton Trans. 47, 3258–3263 (2018). [DOI: 10.1039/C8DT00112J] selected as Outside Front Cover

E. Nakamura
the University of Tokyo
K. Harano
the University of Tokyo

66. Multiple Pathways in the Self-assembly Process of a Pd4L8 Coordination Tetrahedron.

T. Tateishi, T. Kojima, and S. Hiraoka*

Inorg. Chem. 57, 2686–2694 (2018). [DOI: 10.1021/acs.inorgchem.7b03085]

65. Chiral Effects on the Final Step of an Octahedron-Shaped Coordination Capsule Self-Assembly. 

Y. Matsumura, S. Iuchi, S. Hiraoka, and H. Sato*

Phys. Chem. Chem. Phys. 20, 7383–7386 (2018). [DOI: 10.1039/C7CP08237A] selected as Hot Paper and Back Cover

H. Sato
Kyoto University

64. Self-assembly of a Pd4L8 Double-walled Square Partly Takes Place through the Formation of Kinetically Trapped Species.

T. Tateishi, W. Zhu, L. H. Foianesi-Takeshige, T. Kojima, K. Ogata, and S. Hiraoka*

Eur. J. Inorg. Chem. 1192–1197 (2018). [DOI: 10.1002/ejic.201800037]

63. Self-Assembly Process of a Pd2L4 Capsule: Steric Interactions between Neighboring Components Favor the Formation of Large Intermediates

S. Kai, M. Nakagawa, T. Kojima, X. Li, M. Yamashina, M. Yoshizawa, and S. Hiraoka*

Chem. Eur. J. 24, 3965 3969 (2018). [DOI: 1002/chem.201705253] selected as Cover Feature

M. Yoshizawa
Tokyo Institute of Technology

62. Quantitative Analysis of Self-Assembly Process of Hexagonal Pt(II) Macrocyclic Complexes: Effect of Solvent and Components. 

A. Baba, T. Kojima, and S. Hiraoka*

Chem. Eur. J. 24, 838–847 (2018). [DOI: 10.1002/chem.201702955] selected as Hot Paper, Front Cover and Cover Profile

61. Quantitative Analysis of Self-Assembly Process of a Pd2L4 Cage Consisting of Rigid Ditopic Ligands. 

S. Kai, V. Marti-Centelles, Y. Sakuma, T. Mashiko, T. Kojima, U. Nagashima, M. Tachikawa, P. J. Lusby, and S. Hiraoka*

Chem. Eur. J. 24, 663–671 (2018). [DOI: 10.1002/chem.201704285]

P. J. Lusby
University of Edinburgh, UK
M. Tachikawa
Yokohama City University

60. Quantitative Analysis of Self-assembly Process of a Pd12L24 Coordination Sphere. 

S. Kai, T. Shigeta, T. Kojima, and S. Hiraoka*

Chem. Asian J. 12, 3203–3207 (2017). [DOI: 10.1002/asia.201701351]

59. The Effect of Solvent and Coordination Environment of Metal Source on the Self-Assembly Pathway of a Pd(II)-mediated Coordination Capsule. 

S. Kai, Y. Sakuma, T. Mashiko, T. Kojima, M. Tachikawa, and S. Hiraoka*

Inorg. Chem. 56, 12652-12663 (2017). [DOI: 10.1021/acs.inorgchem.7b02152]

58. A Reaction Model on the Self-assembly Process of Octahedron-shaped Coordination Capsules. 

Y. Matsumura, S. Hiraoka, and H. Sato*

Phys. Chem. Chem. Phys. 19, 20338–20342 (2017). [DOI: 10.1039/c7cp03493h]

55. What Do We Learn from the Molecular Self-Assembly Process?

S. Hiraoka*

Chem. Rec. 15, 1144-1147 (2015) [DOI: 10.1002/tcr.201510005]

54. Self-Assembly Process of Dodecanuclear Pt(II)-Linked Cyclic Hexagon.

A. Baba, T. Kojima, and S. Hiraoka

J. Am. Chem. Soc. 137, 7664-7667 (2015). [DOI: 10.1021/jacs.5b04852]



現代化学3, 30–35 (2015).

51. Rate-Determining Step in the Self-Assembly Process of Supramolecular Coordination Capsules. 

Y. Tsujimoto, T. Kojima, and S. Hiraoka* 

Chem. Sci. 5, 4167-4172 (2014). [DOI: 10.1039/C4SC01652A] selected as Back Cover