Configuration of organic dye excimers in nanoporous SiO₂ matrices

The effect of cyanine dye 3,3′-dioctadecyloxacarbocyanine perchlorate (DiO) and benzimidazole dye 4-dimethylamino-1,8-naphthoylene-1′,2′-benzimidazole (DNBI) accumulation in nanoporous silica matrices on the dyes luminescence properties has been studied. For both dyes, ground state dimer formation with perpendicular transition dipoles at high dye concentrations has been considered as a result of restricted geometry of the nanoscale pores. The dimer excitation leads to excimer formation revealing by appearance of new long-wavelength luminescence band and shortening the dye luminescence lifetime. In the excimer luminescence excitation spectra two additional bands have been observed, one of which is bathochromically shifted relatively to the absorption band and another one is hypsocromically shifted. Using the Kasha exciton model it was shown that the excimers possess oblique transition dipoles configuration. - Highlights: • Organic dye molecules are efficiently accumulated in nanoporous silica matrices. • Restricted geometry of SiO₂ nanopores provokes excimerization of both cyanine and benzimidazole dyes. • The excimers reveal configuration of oblique dimers. • The excimers are originated from ground state dimers with a perpendicular arrangement of transition dipoles.