Latex beads are used as a combined template and porogen in the fabrication of monolithic silica containing a hierarchy of pores. Prefabricated core/shell particles, prepared by the layer-by-layer assembly of zeolite (silicalite) nanoparticles onto spherical latex templates, are assembled into macroscopic close-packed structures. Calcination removes all organic components and causes densification of the inorganic structure producing a macroporous zeolite in which both the pore size and wall thickness can be varied.

There are a number of strategies available for extending the length scale of structural organization in inorganic materials. Those that involve the assembly of inorganic nanoparticles into materials with higher-order architecture are collectively termed nanotectonics. In this review, we highlight one possible approach that involves the template-directed assembly of preformed nanoparticle building blocks. The inspiration for the use of preformed particles arises in part from studies of certain biomineral structures, some general aspects of which are summarized. Several synthetic examples of the use of template-directed approaches in nanotectonics are described in detail.

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Crystal tectonics involves the chemical-based construction and self-assembly of organized materials from solid-state building blocks, such as inorganic nanoparticles. This Perspective describes, through a series of examples, how the architectural complexity of materials with higher-order structure can be controlled by organic templating, interparticle molecular recognition and mesophase transformation. It is shown how the coupling of synthesis and self-assembly over multiple length scales is leading to new horizons in the chemistry of organized matter.