Butenolide Derivatives of Biobased Furans: Sustainable Synthetic Dyes.

The dye and pigment manufacturing industry is one of the most polluting in the world. Each year, over one million tons of petrochemical colorants are produced globally, the synthesis of which generates a large amount of waste. Naturally occurring, plant-based dyes, on the other hand, are resource intensive to produce (land, water, energy), and are generally less effective as colorants. Between these two extremes would be synthetic dyes that are fully sourced from biomass-derived intermediates. The present work describes the synthesis of such compounds, containing strong chromophores that lead to bright colors in the yellow to red region of the visible spectrum. The study was originally motivated by an early report of an unidentified halomethylfurfural derivative which resulted from hydrolysis in the presence of barium carbonate, now characterized as a butenolide of 5-(hydroxymethyl)furfural (HMF). The method has been generalized for the synthesis of dyes from other biobased platform molecules, and a mechanism is proposed.

Redox-neutral organocatalytic Mitsunobu reactions.

Nucleophilic substitution reactions of alcohols are among the most fundamental and strategically important transformations in organic chemistry. For over half a century, these reactions have been achieved by using stoichiometric, and often hazardous, reagents to activate the otherwise unreactive alcohols. Here, we demonstrate that a specially designed phosphine oxide promotes nucleophilic substitution reactions of primary and secondary alcohols in a redox-neutral catalysis manifold that produces water as the sole by-product. The scope of the catalytic coupling process encompasses a range of acidic pronucleophiles that allow stereospecific construction of carbon-oxygen and carbon-nitrogen bonds.

High-mobility, trap-free charge transport in conjugated polymer diodes.

Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm2/Vs and a width of the residual tail state distribution comparable to kBT.