Dendritic, nanosized building block for siloxane-based materials: a spherosilicate dendrimer

A spherosilicate dendrimer ( DMS‐1 ) with closely spaced reaction sites (Si? H groups) on the dendrimer surface has been synthesized by stepwise silylation of double‐four‐ring silicate with chlorotriethoxysilane (ClSi(OEt)₃) and subsequently with chlorodimethylsilane (ClSiHMe₂). DMS‐1 consists of a maximum of 40 Si atoms in the interior frameworks and 24 reactive Si? H groups on the surface. Because DMS‐1 is spherical and about 1.5 nm in diameter, it can be regarded as the smallest well‐defined silica‐based nanoparticle. DMS‐1 also forms molecular crystals and is soluble in typical organic solvents. A molecularly ordered silica‐based hybrid can be prepared by heating a cast film of DMS‐1 at 180 °C for 5 days. The surface of DMS‐1 can be modified by hydrosilylation with 1‐hexadecene, triethoxyvinylsilane, and allylic‐terminated tetraethylene glycol monomethyl ether. More than 20 Si? H groups out of 24 react with these reagents. The solubilities of the products depend on the modification. DMS‐1 is not only a building block for nanohybrids, but also the smallest and most precisely designed siloxane‐based nanoparticle.