Daniel T. Chase

6,12-Diarylindeno(1,2-b)fluorenes: Syntheses, Photophysics, and Ambipolar OFETs

Herein we report the synthesis and characterization of a series of 6,12-diarylindeno[1,2-b]fluorenes (IFs). Functionalization with electron donor and acceptor groups influences the ability of the IF scaffold to undergo two-electron oxidation and reduction to yield the corresponding 18- and 22-π-electron species, respectively. A single crystal of the pentafluorophenyl-substituted IF can serve as an active layer in an organic field-effect transistor (OFET). The important finding is that the single-crystal OFET yields an ambipolar device that is able to transport holes and electrons.

Electron-accepting 6,12-diethynylindeno[1,2-b]fluorenes: synthesis, crystal structures, and photophysical properties.

Polycyclic hydrocarbons that possess extended p conjugation are of significant interest because of their potential use in optical and electronic devices such as light emitting devices, field-effect transistors, and photovoltaics. While a majority of studies have focused on acenes such as pentacene and its derivatives (e.g., 1; Scheme 1), these systems are susceptible to oxidative and photolytic degradation; thus, there is a need for alternative, acene-like molecules. One avenue in this search has explored compounds containing five-membered rings, rather than the more traditional six-membered rings. Prime examples of such molecules are dibenzopentalene (2) and derivatives thereof, wherein the groups of Saito, Kawase, and Tilley have recently described improved methods for their construction.

Synthesis and Properties of Fully-Conjugated Indacenedithiophenes

The synthesis and characterization of four fully-conjugated indacenedithiophenes (IDTs) are disclosed. In contrast to anthradithiophenes, regioselective synthesis of both syn and anti isomers is readily achieved. Thiophene fusion imparts increased paratropic character on the central indacene core as predicted by DFT calculations and confirmed by 1H NMR spectroscopy. IDTs exhibit red-shifted absorbance maxima with respect to their all-carbon analogues and undergo two-electron reduction and one-electron oxidation.

Indenofluorenes and derivatives: syntheses and emerging materials applications.

The growing demand for flexible electronic devices and hydrogen storage materials has spurred a resurgence of interest in polyaryl hydrocarbons including graphene, acenes, fullerenes, polythiophenes, etc. Indenofluorenes are another polyaryl molecular scaffold that has shown utility in the organic and hybrid materials arena, with polymers incorporating the indeno[1,2-b]fluorene moiety being common in organic light emitting diodes. This review examines the syntheses and properties of the five distinct indenofluorene regioisomers, with a focus on small molecule applications in organic electronics of this intriguing and somewhat underexplored family of polyaryl hydrocarbons.

Incorporating BODIPY Fluorophores into Tetrakis(arylethynyl)benzenes

Six structural isomers of a tetrakis(arylethynyl)benzene (TAEB) chromophore functionalized with dibutylamine and BODIPY moieties as the corresponding donor and acceptor units were prepared. To evaluate the effectiveness of the donor group, two TAEB molecules and three structurally related bis(arylethynyl)benzene (BAEB) isomers containing only acceptors were also synthesized. The electronic absorption and emission spectra of each series were examined. Additionally, computational studies were employed to corroborate the relative energy levels and gaps present in each series.

Synthesis, crystal structures, and photophysical properties of electron-accepting diethynylindenofluorenediones.

A series of 6,12-bis[(trialkylsilyl)ethynyl]indeno[1,2-b]fluorene-5,11-diones has been synthesized. X-ray crystallographic analysis of these compounds reveals that triisopropylsilyl (TIPS) substitution on the alkyne terminus affords the largest number of intermolecular π-π interactions in the solid state. Conversely, use of trialkylsilyl groups smaller or larger than TIPS furnishes a variety of crystal-packing motifs that contain fewer π-π interactions. Electrochemical and photophysical data suggest that these molecules are excellent electron-accepting materials.

Crystal structures of two unusual, high oxidation state, 16-electron irida-benzenes.

Treatment of an iridabenzene with either bromine or iodine generates high-oxidation-state IrIII iridabenzenes that contain an open coordination site.