Self-assembly of particles into long-range, three-dimensional, ordered superstructures is crucial for the design of a variety of materials, including plasmonic sensing materials, energy or gas storage systems, catalysts and photonic crystals. Here, we have combined experimental and simulation data to show that truncated rhombic dodecahedral particles of the metal–organic framework (MOF) ZIF-8 can self-assemble into millimetre-sized superstructures with an underlying three-dimensional rhombohedral lattice that behave as photonic crystals. Those superstructures feature a photonic bandgap that can be tuned by controlling the size of the ZIF-8 particles and is also responsive to the adsorption of guest substances in the micropores of the ZIF-8 particles. In addition, superstructures with different lattices can also be assembled by tuning the truncation of ZIF-8 particles, or by using octahedral UiO-66 MOF particles instead. These well-ordered, sub-micrometre-sized superstructures might ultimately facilitate the design of three-dimensional photonic materials for applications in sensing.
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Li, F., Josephson, D. P. & Stein, A. Colloidal assembly: the road from particles to colloidal molecules and crystals. Angew. Chem. Int. Ed. 50, 360–388 (2011).
Von Freymann, G., Kitaev, V., Lotsch, B. V . & Ozin, G. A. Bottom-up assembly of photonic crystals. Chem. Soc. Rev. 42, 2528–2554 (2013).
Galisteo-López, J. F. et al. Self-assembled photonic structures. Adv. Mater. 23, 30–69 (2011).
Kim, S.-H., Lee, S. Y., Yang, S.-M. & Yi, G.-R. Self-assembled colloidal structures for photonics. NPG Asia Mater. 3, 25–33 (2011).
Glotzer, S. C. & Solomon, M. J. Anisotropy of building blocks and their assembly into complex structures. Nat. Mater. 6, 557–562 (2007).
Quan, Z. & Fang, J. Superlattices with non-spherical building blocks. Nano Today 5, 390–411 (2010).
Damasceno, P. F., Engel, M. & Glotzer, S. C. Predictive self-assembly of polyhedra into complex structures. Science 337, 453–457 (2012).
Agarwal, U. & Escobedo, F. A. Mesophase behaviour of polyhedral particles. Nat. Mater. 10, 230–235 (2011).
Torquato, S. & Jiao, Y. Dense packings of the Platonic and Archimedean solids. Nature 460, 876–879 (2009).
Sacanna, S. & Pine, D. J. Shape-anisotropic colloids: building blocks for complex assemblies. Curr. Opin. Colloid Interface Sci. 16, 96–105 (2011).
Gantapara, A. P., de Graaf, J., van Roij, R. & Dijkstra, M. Phase diagram and structural diversity of a family of truncated cubes: degenerate close-packed structures and vacancy-rich states. Phys. Rev. Lett. 111, 015501 (2013).
Haji-Akbari, A. et al. Disordered, quasicrystalline and crystalline phases of densely packed tetrahedra. Nature 462, 773–777 (2009).
Ming, T. et al. Ordered gold nanostructure assemblies formed by droplet evaporation. Angew. Chem. Int. Ed. 47, 9685–9690 (2008).
Young, K. L. et al. A directional entropic force approach to assemble anisotropic nanoparticles into superlattices. Angew. Chem. Int. Ed. 52, 13980–13984 (2013).
Henzie, J., Grünwald, M., Widmer-Cooper, A., Geissler, P. L. & Yang, P. Self-assembly of uniform polyhedral silver nanocrystals into densest packings and exotic superlattices. Nat. Mater. 11, 131–137 (2011).
Tao, A. R., Ceperley, D. P., Sinsermsuksakul, P., Neureuther, A. R. & Yang, P. Self-organized silver nanoparticles for three-dimensional plasmonic crystals. Nano Lett. 8, 4033–4038 (2008).
Miszta, K. et al. Hierarchical self-assembly of suspended branched colloidal nanocrystals into superlattice structures. Nat. Mater. 10, 872–876 (2011).
Geuchies, J. J. et al. In situ study of the formation mechanism of two-dimensional superlattices from PbSe nanocrystals. Nat. Mater. 15, 1248–1254 (2016).
Boneschanscher, M. P. et al. Long-range orientation and atomic attachment of nanocrystals in 2D honeycomb superlattices. Science 344, 1377–1380 (2014).
Xie, S. et al. Supercrystals from crystallization of octahedral MnO nanocrystals. J. Phys. Chem. C 113, 19107–19111 (2009).
Volkov, N., Lyubartsev, A. & Bergström, L. Phase transitions and thermodynamic properties of dense assemblies of truncated nanocubes and cuboctahedra. Nanoscale 4, 4765–4771 (2012).
Damasceno, P. F., Engel, M. & Glotzer, S. C. Crystalline assemblies and densest packings of a family of truncated tetrahedra and the role of directional entropic forces. ACS Nano 6, 609–614 (2012).
Park, K. S. et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl Acad. Sci. USA 103, 10186–10191 (2006).
Huang, X.-C., Lin, Y.-Y., Zhang, J.-P. & Chen, X -M. Ligand-directed strategy for zeolite-type metal–organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. Angew. Chem. Int. Ed. 45, 1557–1559 (2006).
Cavka, J. H. et al. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 130, 13850–13851 (2008).
Chen, B., Yang, Z., Zhu, Y. & Xia, Y. Zeolitic imidazolate framework materials: recent progress in synthesis and applications. J. Mater. Chem. A 2, 16811–16831 (2014).
Cravillon, J. et al. Controlling zeolitic imidazolate framework nano- and microcrystal formation: insight into crystal growth by time-resolved in situ static light scattering. Chem. Mater. 23, 2130–2141 (2011).
Cravillon, J. et al. Formate modulated solvothermal synthesis of ZIF-8 investigated using time-resolved in situ X-ray diffraction and scanning electron microscopy. CrystEngComm 14, 492–498 (2012).
Pan, Y. et al. Tuning the crystal morphology and size of zeolitic imidazolate framework-8 in aqueous solution by surfactants. CrystEngComm 13, 6937–6940 (2011).
de Graaf, J., van Roij, R. & Dijkstra, M. Dense regular packings of irregular nonconvex particles. Phys. Rev. Lett. 107, 155501 (2011).
Filion, L. et al. Efficient method for predicting crystal structures at finite temperature: variable box shape simulations. Phys. Rev. Lett. 103, 188302 (2009).
Ahles, M. et al. Spectroscopic ellipsometry on opaline photonic crystals. Opt. Commun. 246, 1–7 (2005).
Zhang, K. et al. Alcohol and water adsorption in zeolitic imidazolate frameworks. Chem. Commun. 49, 3245–3247 (2013).
Schaate, A. et al. Modulated synthesis of Zr-based metal–organic frameworks: from nano to single crystals. Chem. Eur. J. 17, 6643–6651 (2011).
Vermoortele, F. et al. Synthesis modulation as a tool to increase the catalytic activity of metal–organic frameworks: the unique case of UiO-66(Zr). J. Am. Chem. Soc. 135, 11465–11468 (2013).
Wu, H. et al. Unusual and highly tunable missing-linker defects in zirconium metal–organic framework UiO-66 and their important effects on gas adsorption. J. Am. Chem. Soc. 135, 10525–10532 (2013).
This work was supported by EU FP7 ERC-Co 615954, the Spanish MINECO (projects PN MAT2015-65354-C2-1-R and MAT2015-68075-R [SIFE2]) and the Comunidad de Madrid project S2013/MIT-2740 (PHAMA_2.0). It was also funded by the CERCA Programme/Generalitat de Catalunya. The authors based at ICN2 and ICMAB acknowledge the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program (grants SEV-2013-0295 and SEV-2015-0496). The authors thank J. Albalad and J. Saiz for their help in the TGA and reflectance measurements, respectively.
The authors declare no competing financial interests.
About this article
Cite this article
Avci, C., Imaz, I., Carné-Sánchez, A. et al. Self-assembly of polyhedral metal–organic framework particles into three-dimensional ordered superstructures. Nature Chem 10, 78–84 (2018). https://doi.org/10.1038/nchem.2875
Templated interfacial synthesis of metal-organic framework (MOF) nano- and micro-structures with precisely controlled shapes and sizes
Communications Chemistry (2021)
Nature Communications (2021)
Nature Chemistry (2020)
Nature Communications (2020)
A new anionic metal–organic framework with suitable pore and PtS-type topology for selective adsorption and separation of cationic dyes
Chemical Papers (2020)