1. Department of Chemistry & Biochemistry, UCLA, Los Angeles, California 90095-1569, USA

Correspondence to: Sarah H. Tolbert¹ Correspondence and requests for materials should be addressed to S.H.T. (Email: tolbert@chem.ucla.edu).

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material^{1, 2, 3, 4, 5}. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods^{6, 7, 8, 9, 10, 11}, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge₉^4- cluster^{12, 13, 14}, a compound whose use in the synthesis of nanoscale materials is established¹⁵. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement^{16, 17}, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.

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