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Reticular synthesis of porous molecular 1D nanotubes and 3D networks

Abstract

Synthetic control over pore size and pore connectivity is the crowning achievement for porous metal–organic frameworks (MOFs). The same level of control has not been achieved for molecular crystals, which are not defined by strong, directional intermolecular coordination bonds. Hence, molecular crystallization is inherently less controllable than framework crystallization, and there are fewer examples of ‘reticular synthesis’, in which multiple building blocks can be assembled according to a common assembly motif. Here we apply a chiral recognition strategy to a new family of tubular covalent cages to create both 1D porous nanotubes and 3D diamondoid pillared porous networks. The diamondoid networks are analogous to MOFs prepared from tetrahedral metal nodes and linear ditopic organic linkers. The crystal structures can be rationalized by computational lattice-energy searches, which provide an in silico screening method to evaluate candidate molecular building blocks. These results are a blueprint for applying the ‘node and strut’ principles of reticular synthesis to molecular crystals.

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Figure 1: Reticular synthesis of extended frameworks and molecular crystals.
Figure 2: Chiral TCCs as linear ditopic building blocks.
Figure 3: Crystal structures for non-isoreticular homochiral TCC1-R and TCC2-R and gas-sorption isotherms for TCC1-R, TCC2-R and TCC3-R.
Figure 4: Synthesis of ‘isoreticular’ racemic 1D nanotubes.
Figure 5: Predicted crystal-energy landscapes.
Figure 6: Reticular synthesis of pillared porous molecular networks by mixing linear ditopic cages and tetrahedral cages with opposing chirality.

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Acknowledgements

We acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) (grants EP/H000925/1, EP/N004884/1 and EP/K018132/1) and the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC through grant agreements no. 307358 (ERC-stG-2012-ANGLE) and no. 321156 (ERC-AG-PE5-ROBOT). K.E.J. and T.H. thank the Royal Society for University Research Fellowships. We thank Diamond Light Source for access to beamlines I19 (MT8728, and MT11231) and I11 (EE12336), which contributed to the results presented here, and M. Warren and S. Barnett for their assistance. We thank the Advanced Light Source, supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract no. DE-AC02-05CH11231, and S. J. Teat and K. J. Gagnon for their assistance. We acknowledge the ARCHER UK National Supercomputing Service via UK's HPC Materials Chemistry Consortium membership, which is funded by the EPSRC (EP/L000202), as well as the use of the IRIDIS High Performance Computing Facility and associated support services at the University of Southampton, in the completion of this work. We thank M. Jones and the Centre for Materials Discovery for assistance with liquid chromatography–mass spectroscopy measurements and D. McMahon for assistance with powder-pattern similarity calculations.

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Authors and Affiliations

Authors

Contributions

A.G.S. and A.I.C. conceived the project. A.G.S., M.E.B., X.W., G.C. and C.M. prepared the precursors and cage molecules. A.G.S., C.M. and M.A.L. crystallized and co-crystallized the cage molecules. M.A.L. and S.Y.C. interpreted the X-ray data. R.C., T.H. and L.C. interpreted the sorption data. A.P. and G.M.D. carried out and interpreted the CSP calculations. K.E.J. modelled the cage conformers and carried out and interpreted gas-phase dimer calculations. D.H. constructed and interpreted the variable pore-size-distribution models. All the authors interpreted the structures and contributed to the preparation of the manuscript.

Corresponding authors

Correspondence to G. M. Day or A. I. Cooper.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 9754 kb)

Supplementary information

Crystallographic data for TCC1-R·MeOH solvate. (CIF 2450 kb)

Supplementary information

Crystallographic data for TCC2-R·MeOH solvate. (CIF 1589 kb)

Supplementary information

Crystallographic data for TCC2-R·NMP·MeOH solvate. (CIF 1156 kb)

Supplementary information

Crystallographic data for TCC2-R·NMP·MeOH solvate 300K. (CIF 1142 kb)

Supplementary information

Crystallographic data for Racemic TCC1·Et2O solvate. (CIF 3239 kb)

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Crystallographic data for Racemic TCC2·IPA solvate. (CIF 4616 kb)

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Crystallographic data for Racemic TCC2·acetone solvate. (CIF 6079 kb)

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Crystallographic data for Racemic TCC2·acetone solvate 150K. (CIF 1292 kb)

Supplementary information

Crystallographic data for Racemic TCC2 desolvate 350K. (CIF 982 kb)

Supplementary information

Crystallographic data for Racemic TCC2 desolvate 150K. (CIF 1228 kb)

Supplementary information

Crystallographic data for Racemic TCC3·Et2O solvate. (CIF 2457 kb)

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Crystallographic data for Racemic TCC3 solvate 300K. (CIF 1176 kb)

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Crystallographic data for Racemic TCC3 desolvate 350K. (CIF 817 kb)

Supplementary information

Crystallographic data for Racemic TCC3·N2. (CIF 2457 kb)

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Crystallographic data for TCC2-S·TCC3-R·dioxane solvate. (CIF 5589 kb)

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Crystallographic data for TCC2-R·2(CC3-S)·dioxane solvate. (CIF 11276 kb)

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Crystallographic data for TCC2-R·2(CC3-S) desolvate 293K. (CIF 5979 kb)

Supplementary information

Crystallographic data for TCC1-R·2(CC3-S)·dioxane solvate 150K. (CIF 15167 kb)

Supplementary information

Crystallographic data for TCC1-R·2(CC3-S) desolvate 400K. (CIF 3591 kb)

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Slater, A., Little, M., Pulido, A. et al. Reticular synthesis of porous molecular 1D nanotubes and 3D networks. Nature Chem 9, 17–25 (2017). https://doi.org/10.1038/nchem.2663

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