We have previously demonstrated that solution-cast films of conjugated polymers with grafted alkyl side chains comprise clearly identifiable domains ca. 10 nm in size upon solvent evaporation. Here we show that these nanodomains indeed serve as basic units for morphological development in poly(9,9-di-n-octyl-2,7-fluorene) (PFO) films during cold crystallization. Results of our microscopic and diffraction observations indicate that the cold crystallization process involves intradomain nucleation and growth, followed by nanodomain alignment and coalescence into fibrils in the sub-micrometer length scale via thermally activated adjustment of nanodomain orientation. An analogy with oriented aggregation (or oriented attachment-coalescence) behavior of nanocrystals of metal oxides is drawn; the relevance to recently proposed models of polymer crystallization via primary nucleation induced at the growth front is addressed.
While it is known that the chain length strongly affects the properties of π-conjugated polymers, the effects of chain length on the molecular structure, chain conformation, and oxidation state properties in donor−acceptor-type conjugated structures remain unclear. This limits our understanding of how the polymer molecular weight impacts material properties. Here, a discrete and monodisperse oligomer series (n = 3, 5, 7, 9, 15, and 21) and polymers (nPB), composed of the donor 3,4propylenedioxythiophene (ProDOT), the acceptor benzothiadiazole (BTD), and methylthio end-capping groups, are synthesized by C−H-activated cross-coupling. The molecular structure, molecular weight, and dispersity of each oligomer/polymer are thoroughly characterized by nuclear magnetic resonance spectroscopy, mass spectrometry, and gel permeation chromatography. This series reveals a rod-to-coil transition at n = 15 and coil formation at polymer length scales of ∼28 units via solution small-angle neutron scattering characterization. The oxidation states are deciphered via cyclic voltammetry, differential pulse voltammetry, spectroelectrochemistry, and density functional theory calculations. Oligomers 3−9 undergo successive one-electron oxidation steps, while 15 and higher undergo multielectron oxidations per step in CH 2 Cl 2 −TBAPF 6 at a Pt ultramicroelectrode. The electronic transition of each oxidation state (1+, 2+, 3+, etc.) is tracked by absorption spectroscopy, revealing a "bipolaron to di-polaron" transition at n = 7 at which shorter oligomers prefer bipolaron formation and longer oligomers prefer di-polaron formation in their dication states. Furthermore, oxidized 15 has a lower electronic transition energy compared to its polymer homologue, as shown by spectroelectrochemistry, revealing a synergy between the chain length and the oxidation state properties. This study proves that the convergence limit between small molecule and polymer behavior occurs at approximately 15 units and highlights the property transitions that occur as a function of chain length for a donor−acceptor class of conjugated organic materials.
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