Controlled Formation of the Two-Dimensional TTBC J-Aggregates in an Aqueous Solution

Abstract

Strong experimental and theoretical evidence was provided on the controlled formation of the two-dimensional J-aggregates that were assembled in the herringbone morphology. The exciton-band structure formation of 1,1′,3,3′-tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (TTBC) J-aggregates was investigated in ionic (NaOH) aqueous solution at room temperature. The control was achieved by changing the [TTBC] ata given [NaOH], or vice versa, and was monitored through the changes in the absorption, fluorescence excitation, and emission spectra. Specific attention was paid to expose the excited-state structure and dynamics through simulations of the excitonic properties, which included diagonal energetic disorder and phononassisted exciton relaxation. Aggregates were characterized by an asymmetrically split Davydov pair, an H-band ( 500 nm, 1300 cm -1wide, Lorentzian-like) and a J-band ( 590 nm, 235 cm -1wide, with a band shapetypical of a one-dimensional J-aggregate), whose relative intensities showed a strong dependence on the [TTBC]/[NaOH]. The H-band is favored by high [TTBC] or high [NaOH]. An explanation of the control on the aggregate formation was given by correlating the changes in the absorption with the structural modifications and the subsequent changes in the dynamics, which were induced by variations in the dye and NaOH concentrations. The J-band shape/width was attributed to disorder and disorder-induced intraband phononassisted exciton relaxation. The intraband processes in both bands were estimated to occur in the same time scale (about a picosecond). It has been suggested that the wide energetic gap between the Davydov split bands (3000 cm -1 ) could get bridged by the excitonic states of the loosely coupled chains, in addition to the monomeric species at low [TTBC]. Phonon-assisted interband relaxation, through the band gap states and/or directly from the H- to the J-band, are suggested for accounting the difference between the bandwidths and shapes of the two bands. Energy transfer between the H-band and the monomeric species is suggested as crucial for tuning the relative strengths of the two bands.