Hierarchial coassembly of a cyanine dye in poly(vinyl alcohol) fibrous films by electrospinning.

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 parallel-positioned 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.