Chapter 11
Layered Hydrogen-Bonded Organic
Frameworks as Highly Crystalline
Porous Materials
Ichiro Hisaki, Qin Ji, Kiyonori Takahashi, and Takayoshi Nakamura
Abstract Porous molecular crystals (PMCs) with well-defined, self-standing pores
have been attracted much attention due to significant functionality provided by
selective and reversible inclusion of certain chemical species into the pores. PMCs
constructed through preorganized hydrogen bonds (H-bonds) are specifically called
as hydrogen-bonded organic frameworks (HOFs). For recent two decades, HOFs
have been intensively explored. HOFs are frequently obtained as single crystals,
which is convenient to reveal the structure–property relationship. Their regenerable and reusable features are also appealing. However, HOFs are relatively
fragile, and their designing strategy needs to be more considered compared with
other porous frameworks because of weakness of H-bonds. Regarding this, we
have demonstrated that C 3 -symmetric π-conjugated molecules (C 3 PIs) possessing
o-bis(4-carboxyphenyl)benzene moieties in their periphery give layered frameworks
composed of isostructural H-bonded hexagonal networks (H-HexNets) and that
the frameworks can effectively provide stable, robust, multifunctional HOFs with
permanent porosity. The frameworks also can work as a platform to achieve very
unique alignment of functional molecules such as C 60 . Our strategy for constructing
functional HOFs contributes to developing a new field of porous organic materials.
Keywords Porous molecular crystal · Hydrogen-bonded organic framework ·
π-conjugated molecule · Carboxylic acid · Permanent porosity
I. Hisaki (B) · K. Takahashi · T. Nakamura
Research Institute for Electronic Science, Hokkaido University, N20W10, Sapporo, Hokkaido
001-0020, Japan
e-mail: hisaki@chem.es.osaka-u.ac.jp
I. Hisaki · Q. Ji · K. Takahashi · T. Nakamura
Graduate School of Environmental Science, Hokkaido University, N10W5, Sapporo, Hokkaido
060-0810, Japan
Present Address:
I. Hisaki
Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka,
Osaka 560-8531, Japan
© 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_11
199
Layered Hydrogen-Bonded Organic
Frameworks as Highly Crystalline
Porous Materials
Ichiro Hisaki, Qin Ji, Kiyonori Takahashi, and Takayoshi Nakamura
Abstract Porous molecular crystals (PMCs) with well-defined, self-standing pores
have been attracted much attention due to significant functionality provided by
selective and reversible inclusion of certain chemical species into the pores. PMCs
constructed through preorganized hydrogen bonds (H-bonds) are specifically called
as hydrogen-bonded organic frameworks (HOFs). For recent two decades, HOFs
have been intensively explored. HOFs are frequently obtained as single crystals,
which is convenient to reveal the structure–property relationship. Their regenerable and reusable features are also appealing. However, HOFs are relatively
fragile, and their designing strategy needs to be more considered compared with
other porous frameworks because of weakness of H-bonds. Regarding this, we
have demonstrated that C 3 -symmetric π-conjugated molecules (C 3 PIs) possessing
o-bis(4-carboxyphenyl)benzene moieties in their periphery give layered frameworks
composed of isostructural H-bonded hexagonal networks (H-HexNets) and that
the frameworks can effectively provide stable, robust, multifunctional HOFs with
permanent porosity. The frameworks also can work as a platform to achieve very
unique alignment of functional molecules such as C 60 . Our strategy for constructing
functional HOFs contributes to developing a new field of porous organic materials.
Keywords Porous molecular crystal · Hydrogen-bonded organic framework ·
π-conjugated molecule · Carboxylic acid · Permanent porosity
I. Hisaki (B) · K. Takahashi · T. Nakamura
Research Institute for Electronic Science, Hokkaido University, N20W10, Sapporo, Hokkaido
001-0020, Japan
e-mail: hisaki@chem.es.osaka-u.ac.jp
I. Hisaki · Q. Ji · K. Takahashi · T. Nakamura
Graduate School of Environmental Science, Hokkaido University, N10W5, Sapporo, Hokkaido
060-0810, Japan
Present Address:
I. Hisaki
Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka,
Osaka 560-8531, Japan
© 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_11
199