Lamellar mono-amidosil hybrids incorporating monomethinecyanine dyes

摘要

Mono-amide cross-linked alkyl-siloxane hybrids synthesized through the sol-gel process and the self-directed assembly have been doped with variable concentrations of monomethinecyanines SSCH2(C6H5) I, SSCH3CI and SSC2H5ClO4. The host matrix m-A(14) is a lamellar structured hybrid composed of short methyl-capped alkyl chains grafted to the siliceous framework through amide groups. The doped mono-amidosil hybrid materials were obtained as solid powders. The bulky SSCH2(C6H5)I dye inhibited the condensation of the silica network. In the SSCH3CI- and SSC2H5ClO4-doped m-A(14)-based materials the original lamellar structure coexists with a new lamellar ordered phase with a lower interlamellar distance in which the alkyl chains adopt essentially all-trans conformations. The efficient encapsulation of these two dyes by m-A(14), which ensures their complete dissolution, is due to the coordination of the S atoms of SSCH3CI and SSC2H5ClO4 to the carbonyl oxygen atoms of the amide cross-links. This process leads to a major breakdown of the disordered and ordered hydrogen-bonded aggregates of m-A(14), but does not affect globally the strength of the hydrogen-bonded array. The most dilute SSC2H5ClO4-doped mono-amidosil studied displays room temperature emission in the visible spectral region (380-680 nm) due to the convolution of the intrinsic emission (blue spectral region) of m-A(14) with that of the SSC2H5ClO4 dye (green and red spectral regions) due to the formation of fluorescent J-dimers. The excitation spectra (monitored along the emission spectra) reveal the occurrence of host-to-monomethinecyanine energy transfer.