Luminescence properties of the mixed J-aggregate of oxacyanine dye and thiacyanine dye. Formation of a persistence-type aggregate

The monolayer assemblies incorporating the J-aggregates of oxacyanine dye, N,N'-dioctadecyloxacyanine perchlorate (S9), and thiacyanine dye, N,N'-dioctadecylthiacyanine perchlorate (S11), S9(J) + S11(J), have been fabricated by the Langmuir-Blodgett (LB) technique. The mole fraction X of S 11, X = [S11]/([S9] + [S I I I), was varied from 0 to 1. Steady-state absorption spectra, fluorescence spectra, and picosecond fluorescence decay curves of the monolayer assemblies have been measured. Spectroscopic properties of the monolayer assemblies incorporating the individual dye aggregates, S9 J-aggregate (S9(J), X = 0) or S I I J-aggregate (S11(J), X = 1), are characterized by a distinct J-band and resonance fluorescence at,lambda(ab) = 403 nm and lambda(e)m = 403 nm for S9(J) and lambda(ab) = 456 nm and lambda(em) = 463 nm for S I I (J). On the other hand, absorption spectra of the S9(J) + S I I (J) assemblies for X = 0.1-0.9 display two absorption bands, a shorter wavelength one and a longer wavelength one, whose peak positions are blue-shifted from those of the corresponding J-bands of the S9 J-aggregate and the S I I J-aggregate, respectively. Furthermore, fluorescence spectra are characterized by a single band (longer wavelength fluorescence) which is somewhat blue-shifted from the resonance fluorescence of the S I I J-aggregate. The fluorescence lifetimes of the S I I J-aggregate and isolated SI I molecules in LB films appear to be tau = I 10 and 1900 ps, respectively, while the fluorescence lifetime of the longer wavelength fluorescence of the S9(J) + S 1 I(J) assemblies takes practically a constant value of tau = 170-180 ps for X = 0.2-0.8. These observations would indicate that S9 and S I I molecules in the S9(J) + S I I (J) assembly can form a specific mixed aggregate distinct from the individual S9 and S 11 J-aggregates. From detailed considerations of the former works on luminescence properties of the S9 J-aggregate doped with isolated S I I molecules, as well as the mosaic-type mixed J-aggregate (M-aggregate) composed of a certain thiacyanine dye, 3,3'-disulfopropyl-5,5'-dichlorothiacyanine sodium salt, and thiacarbocyanine dye, meso-substituted 3,3'-disulfopropyl-5,5'-dichlorothiacarbocyanine potassium salt, it is suggested that S9 and S I I can form a homogeneous aggregate of the persistence type (HP-aggregate). The HP-aggregate is distinguished from the M-aggregate because it is characterized by homogeneous mixing of two component dyes and persistence of two absorption bands.