Structure and photoluminescent features of di-amide cross-linked alkylene–siloxane hybrids

Abstract

Novel amide cross-linked alkylene-siloxane hybrid materials (di-amidosils) synthesized by the sol-gel process have been investigated. Two samples identified by the notation d-A(x) with x = 4 and 8 (where x is the number of methylene groups of the alkylene chain) have been produced as transparent, amorphous, rigid monoliths. The d-A(8) material is thermally stable up to approximately 245°C. In this hybrid the siliceous framework is mainly composed of [-(CH2)Si(OSi)3)] and [-(CH 2)Si(OSi)2(OH)] substructures. Structural unit distances of 4.1 and 4.2 A and average interparticle distances of 12 and 17 A have been determined for d-A(4) and d-A(8), respectively. In these compounds the alkylene chains are disordered and adopt gauche conformations. While a negligible proportion of the amide linkages remain non-bonded, the great majority of these groups belong to highly disordered strong hydrogen-bonded amide-amide associations. The hybrids introduced are room temperature white light emitters, presenting an intense, broad emission band in the blue/purplish-blue spectral region. The origin of such a band has been ascribed to the convolution of donor-acceptor pair (D-A) recombinations that occur in the NH groups of the amide linkages and in the siliceous nanodomains. The maximum quantum yield value of the d-A(8) di-amidosil is 5.4%.