Exciton Coupling of Merocyanine Dyes from H- to J-type in the Solid State by Crystal Engineering.

A key issue for the application of π-conjugated organic molecules as thin film solid-state materials is the packing structure, which drastically affects optical and electronic properties due to intermolecular coupling. In this regard, merocyanine dyes usually pack in H-coupled antiparallel arrangements while structures with more interesting J-type coupling have been rarely reported. Here we show that for three highly dipolar merocyanine dyes, which exhibit the same π-scaffold and accordingly equal properties as monomers in solution, the solid-state packing can be changed by a simple variation of aliphatic substituents to afford narrow and intense absorption bands with huge hypsochromic (H) or bathochromic (J) shifts for their thin films and nanocrystals. Time-dependent density functional theory calculations show that the energetic offset of almost 1 eV magnitude results from distinct packing motifs within the crystal structures that comply with the archetype H- or J-aggregate structures as described by Kasha's exciton theory.

Conformational Switching of π-Conjugated Junctions from Merocyanine to Cyanine States by Solvent Polarity.

Directed by the solvent polarity, the prevalent conformation of a polymethine dye bearing a branched π-conjugated junction can be switched from a heptamethine donor-acceptor (DA) merocyanine-type π-conjugated system to a nonamethine DAD cyanine-type π-conjugated scaffold. Concomitantly the absorption maximum shifts from 585 nm in dichloromethane to 748 nm in methanol solution.

Influence of Solid-State Packing of Dipolar Merocyanine Dyes on Transistor and Solar Cell Performances.

A series of nine dipolar merocyanine dyes has been studied as organic semiconductors in transistors and solar cells. These dyes exhibited single-crystal packing motifs with different dimensional ordering, which can be correlated to the performance of the studied devices. Hereby, the long-range ordering of the dyes in staircase-like slipped stacks with J-type excitonic coupling favors charge transport and improves solar cell performance. The different morphologies of transistor thin films and solar cell active layers were investigated by UV-vis, AFM, and XRD experiments. Selenium-containing donor-acceptor (D-A) dimethine dye 4 showed the highest hole mobility of 0.08 cm(2) V(-1) s(-1). BHJ solar cells based on dye 4 were optimized by taking advantage of the high crystallinity of the donor material and afforded a PCE of up to 6.2%.