11 Layered Hydrogen-Bonded Organic …
217
composed of C 3 -symmetric π-conjugated molecules (C 3 PIs) possessing three obis(4-carboxyphenyl)benzene moieties in the periphery. Thanks to the triangular
H-bonded motif named phenylene triangle (PhT), C 3 PIs can form isostructural HHexNet sheets, which further stack via secondary intermolecular interactions such
as a π/π interaction to give layered HOFs. Moreover, we revealed that even bowlshaped C 3 PI form H-bonded, 2D networked structures, in which all of carboxy groups
satisfied through formation of H-bonded dimer. These results can make us realize
promising potentials of HOFs. Once the construction ways of HOFs have been established, the properties and functionality of HOFs begin to be investigated. As reported
by Cooper and Day, high-throughput exploration for development of functional
porous materials is becoming possible by combining with theoretical calculation
and robotics [63]. We hope that we would report multifunctional HOFs in the near
future.
References
1. Allcock, H.R., Siegel, L.A.: Phosphonitrilic compounds. III. Molecular inclusion compounds
of tris(o-phenylenedioxy)phosphonitrile trimer. J. Am. Chem. Soc. 86, 5140–5144 (1964)
2. Sozzani, P., Comotti, A., Simonutti, R., Meersmann, T., Logan, J.W., Pines, A.: A porous
crystalline molecular solid explored by hyperpolarized xenon. Angew. Chem. Int. Ed. 39,
2695–2698 (2000)
3. Sozzani, P., Bracco, S., Comotti, A., Ferretti, L., Simonutti, R.: Methane and carbon dioxide
storage in a porous van der Waals crystal. Angw. Chem. Int. Ed. 44, 1816–1820 (2005)
4. Atwood, J.L., Davies, J.E.D., MacNicol, D.D. (eds.): Inclusion Compounds, vol. 1–3. Academic
Press, London (1984)
5. Barbour, L.J.: Crystal porosity and the burden of proof. Chem. Comm. 1163–1168 (2006)
6. Tian, J., Thallapally, P.K., McGrail, B.P.: Porous organic molecular materials. CrystEngComm
14, 1909–1919 (2012)
7. Mastalerz, M.: Permanent Porous materials from discrete organic molecules—towards ultrahigh surface areas. Chem. Eur. J. 18, 10082–10091 (2012)
8. Atwood, J.L., Barbour, L.J., Jerga, A.: Storage of methane and freon by interstitial van der
Waals confinement. Science 296, 2367–2369 (2002)
9. Adach, T., Ward, M.D.: Versatile and resilient hydrogen-bonded host frameworks. Acc. Chem.
Res. 49, 2669–2679 (2016)
10. Lu, J., Cao, R.: Porous organic molecular frameworks with extrinsic porosity: a platform for
carbon storage and separation. Angew. Chem. Int. Ed. 55, 9474–9480 (2016)
11. Luo, J., Wang, J.-W., Zhang, J.-H., Lai, S., Zhong, D.-C.: Hydrogen-bonded organic frameworks: design, structures and potential applications. Zhong, CrystEngComm 20, 5884–5898
(2018)
12. Lin, R.-B., He, Y., Li, P., Wang, H., Zhou, W., Chen, B.: Multifunctional porous hydrogenbonded organic framework materials. Chen. Chem. Soc. Rev. 48, 1362–1389 (2019)
13. Hisaki, I., Chen, X., Takahashi, K., Nakamura, T.: Designing hydrogen-bonded organic
frameworks (HOFs) with permanent porosity. Angew. Chem. Int. Ed. 58, 11160–11170 (2019)
14. He, Y., Xiang, S., Chen, B.: A microporous hydrogen-bonded organic framework for highly
selective C 2 H 2 /C 2 H 4 separation at ambient temperature. J. Am. Chem. Soc. 133, 14570–14573
(2011)
15. Maly, K.E., Gagnon, E., Maris, T., Wuest, J.D.: Engineering hydrogen-bonded molecular crystals built from derivatives of hexaphenylbenzene and related compounds. J. Am. Chem. Soc.
129, 4306–4322 (2007)
217
composed of C 3 -symmetric π-conjugated molecules (C 3 PIs) possessing three obis(4-carboxyphenyl)benzene moieties in the periphery. Thanks to the triangular
H-bonded motif named phenylene triangle (PhT), C 3 PIs can form isostructural HHexNet sheets, which further stack via secondary intermolecular interactions such
as a π/π interaction to give layered HOFs. Moreover, we revealed that even bowlshaped C 3 PI form H-bonded, 2D networked structures, in which all of carboxy groups
satisfied through formation of H-bonded dimer. These results can make us realize
promising potentials of HOFs. Once the construction ways of HOFs have been established, the properties and functionality of HOFs begin to be investigated. As reported
by Cooper and Day, high-throughput exploration for development of functional
porous materials is becoming possible by combining with theoretical calculation
and robotics [63]. We hope that we would report multifunctional HOFs in the near
future.
References
1. Allcock, H.R., Siegel, L.A.: Phosphonitrilic compounds. III. Molecular inclusion compounds
of tris(o-phenylenedioxy)phosphonitrile trimer. J. Am. Chem. Soc. 86, 5140–5144 (1964)
2. Sozzani, P., Comotti, A., Simonutti, R., Meersmann, T., Logan, J.W., Pines, A.: A porous
crystalline molecular solid explored by hyperpolarized xenon. Angew. Chem. Int. Ed. 39,
2695–2698 (2000)
3. Sozzani, P., Bracco, S., Comotti, A., Ferretti, L., Simonutti, R.: Methane and carbon dioxide
storage in a porous van der Waals crystal. Angw. Chem. Int. Ed. 44, 1816–1820 (2005)
4. Atwood, J.L., Davies, J.E.D., MacNicol, D.D. (eds.): Inclusion Compounds, vol. 1–3. Academic
Press, London (1984)
5. Barbour, L.J.: Crystal porosity and the burden of proof. Chem. Comm. 1163–1168 (2006)
6. Tian, J., Thallapally, P.K., McGrail, B.P.: Porous organic molecular materials. CrystEngComm
14, 1909–1919 (2012)
7. Mastalerz, M.: Permanent Porous materials from discrete organic molecules—towards ultrahigh surface areas. Chem. Eur. J. 18, 10082–10091 (2012)
8. Atwood, J.L., Barbour, L.J., Jerga, A.: Storage of methane and freon by interstitial van der
Waals confinement. Science 296, 2367–2369 (2002)
9. Adach, T., Ward, M.D.: Versatile and resilient hydrogen-bonded host frameworks. Acc. Chem.
Res. 49, 2669–2679 (2016)
10. Lu, J., Cao, R.: Porous organic molecular frameworks with extrinsic porosity: a platform for
carbon storage and separation. Angew. Chem. Int. Ed. 55, 9474–9480 (2016)
11. Luo, J., Wang, J.-W., Zhang, J.-H., Lai, S., Zhong, D.-C.: Hydrogen-bonded organic frameworks: design, structures and potential applications. Zhong, CrystEngComm 20, 5884–5898
(2018)
12. Lin, R.-B., He, Y., Li, P., Wang, H., Zhou, W., Chen, B.: Multifunctional porous hydrogenbonded organic framework materials. Chen. Chem. Soc. Rev. 48, 1362–1389 (2019)
13. Hisaki, I., Chen, X., Takahashi, K., Nakamura, T.: Designing hydrogen-bonded organic
frameworks (HOFs) with permanent porosity. Angew. Chem. Int. Ed. 58, 11160–11170 (2019)
14. He, Y., Xiang, S., Chen, B.: A microporous hydrogen-bonded organic framework for highly
selective C 2 H 2 /C 2 H 4 separation at ambient temperature. J. Am. Chem. Soc. 133, 14570–14573
(2011)
15. Maly, K.E., Gagnon, E., Maris, T., Wuest, J.D.: Engineering hydrogen-bonded molecular crystals built from derivatives of hexaphenylbenzene and related compounds. J. Am. Chem. Soc.
129, 4306–4322 (2007)