We report molecular aggregate formation of TTBC (1,1′,3,3′-tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine) in submicrometer-sized PVA (poly-(vinyl alcohol)) fibers by electrospinning. The formation of the molecular aggregate is examined by solution and instrumental parameters of electrospinning. The precursor solution of PVA/TTBC, in the range of 0.016−0.065 wt % is subjected to electrospinning under an electrical field ranging from 0.95 to 1.81 kV cm −1 . Both randomly deposited and uniaxially aligned fibers are achieved by using two parallelpositioned metal strips as counter electrode. Photoluminescence and polarized Fourier transform infrared spectroscopies are employed to determine spectral properties of the fibers. H-aggregates are formed within the electrospun fibers, regardless of their alignment, and H-and J-type aggregates coexist in the alternative spin-coated and the cast films. A strongly polarized photoluminescence emission is observed in the direction of uniaxially aligned fibers as a result of the orientation of the H-aggregates along the fiber axis. We demonstrate that electrospinning is a process capable of forming and orienting TTBC aggregates during the structural development of the polymer/dye nanofibers. These fibrous films may potentially find applications in optics and electronics.
■ INTRODUCTIONMolecular aggregates of dyes have attracted remarkable interest because they exhibit collective optical/excitonic properties with various functions. The strong coupling of transition dipoles of the constituent dye molecules which have internal molecular arrangement within the aggregate leads to delocalized excitonic states over a few to several molecules and, accordingly, the enhancement of the optical properties. 1 The aggregation patterns of the dye molecules exhibit red shift (J-type) and blue shift (H-type) in absorption bands. 2,3 TTBC is a twodimensional planar molecule that can form secondary interactions, yielding intriguing supramolecular structure. This cyanine dye undergoes both H-and J-type aggregation by shortrange noncovalent interactions, such as dipole−dipole interactions, π−π stacking, and hydrogen bonding. Aggregation is driven mainly by the presence of a strong transition dipole moment formed by conjugated π-electrons of the polymethine backbone of cyanine dyes. 4 The construction of sophisticated molecular dye assemblies and highly ordered dye aggregates plays a significant role in designing smart materials because their optical properties show alteration depending on the structural organization of the dyes. 5 The understanding of internal organization and controlling the mesoscopic morphology of cyanine aggregates has provided a powerful way of developing techniques for fabrication of functional structures designed for specific purposes. To date, a number of approaches have been demonstrated to form and align the aggregates, such as magnetic field, 6−9 vertical spin coating, 10−12 Langmuir−Blodgett films, 13,14 adsorption on a single crystal surface, 15,16 ...