We demonstrate asimple method to create avariety of silica-based colloidal molecules through the covalent assembly of site-specifically functionalizedp atchy nanoparticles with complementary nanospheres.Colloidal analogues of BeBr 2 ,BBr 3 and CBr 4 are obtained from sp-, sp 2 -and sp 3 -like particles,while Br 2 Oand NBr 3 analogues can be fabricated by varying the relative amounts of both colloidal precursors.W e also show that it is possible to attach covalently silica nanospheres of various sizes to one central patchy nanoparticle, which leads to the formation of more complex colloidal molecules,i ncluding chiral ones.T he possibility to easily extend the strategy to other colloidal precursors whichc an serve as satellites,for example,ellipsoidal polymer particles or metallic nanoparticles,o pens the way to ar ich variety of new colloidal analogues of atoms whichc ould serve as building blocks of next generation materials.

We report a new route to synthesize clusters, or so-called colloidal molecules (CMs), which mimic the symmetry of molecular structures made of one central atom. We couple site-specifically functionalized patchy nanoparticles, i.e., valence-endowed colloidal atoms (CAs), with complementary nanospheres through amide bonds. By analogy with the Gillespie formalism, we show that AX4, AX3E1 and AX2E2 CMs can be obtained from tetravalent sp3-like CAs when the relative amount of both building units is varied in a controlled manner. We obtain AX2 CMs from divalent sp-like CAs. We also show that it is possible to covalently attach two different types of satellites to the same central patchy nanoparticle to create more complex CMs, opening the way to the fabrication of new multifunctional nanostructures with well-controlled shape and composition.