High‐Yielding Synthesis and Full Spectroscopic Characterization of 5,6:11,12‐Di‐o‐phenylenetetracene and Its Synthesis Intermediates

Abstract

Herein we present a synthetic gram-scale route to 5,6:11,8), which is a member of the class of cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). Full analytical characterization of the title compound was carried out by IR, Raman, UV/Vis, and high-field 1 H NMR spectroscopy, as well as by mass spectrometry. A unique double-elimination of phenylide moieties, as the key reaction step, gave DOPT for the first time in high purity and

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12‐di‐o‐Phenylenetetracene

“…Finally,w eg ive evidence towards the dependence of its electronic thin film transistor properties on the deposited film density.A ccording to our finding,r eductive elimination of two phenyl rings from the dihydrotetracene derivative 5,12-diphenyl-5,6;11,12-di-o-phenylene-5,12-dihydrotetracenepseudorubrene) 1 under re-aromatization has yielded DOPT 2 in high yield on ag ram scale. [5] As an extension of these studies we now report on the molecular structure of 2.W ehave found that it crystallizes at least in two polymorphic crystal arrangements depending on the crystallization procedures employed. Growth from aconcentrated tetrahydrofuran or toluene solution gives single crystals of DOPT which crystallize in space group C 2/c, whereas slow thermal gradient sublimation gives deep blue, primitive monoclinic crystals of space group P 2 1 /n (see Supporting Information).…”

“…[1,2] In the group of cyclo-pentafused polycyclica romatic hydrocarbons (PAH) 2 represents aprototypical acene framework molecule with peri-substitution closely related to tetracene,5,6,11,12-tetraphenyltetracenerubrene,orthe di-ophenylene substituted anthracene molecule rubicene. [2] Although, reported earlier in elusive experimental work [3] it was only very recently,that DOPT 2 was made accessible by Murata [4] and our group [5] in two independent and straightforward high yield synthetic approaches.Murata et al presented ag eneral approach towards cyclo-pentafused polycyclic aromatics including DOPT-derivatives starting from the 5,11-diaryl-tetracene framework.[4] Shortly after,w ew ere able to devise agram-scale synthesis based on well established Diels-Alder chemistry for the parent molecule DOPT introducing as of ar unprecedented reductive double phenyl elimination.[5] Highly condensed PA Hm olecules like DOPT with their oftentimes energetically favorable molecular orbital ordering with small electronic band gap differences excel themselves as promising semiconducting organic materials for controlled charge transport. Thea fore mentioned close structural relationship of DOPT to the polyacene aromatic family especially the parent tetracene might promise interesting functional properties applicable in organic electronics like thin film transistors or future solar energy harvesting devices.…”

“…[7] Moreover the fact that DOPT 2 is able to accept at least up to two electrons [4,5] manifests its high electron affinity and makes it potentially suited for organic semiconductor applications.I n this regard it falls into the same class of electroactive molecules as indenofluorenes,emaraldicenes or (silylethynylated) extended p-systems which have been proven as electron accepting as well as ambipolar molecules in organic Figure 1. Left:Superordinated structure of 5,6;11,2)a sf ound in e.g.,t he D 2d isomer of the geodesic fullerene C84. Right:Illustration of the all-planar cruciform structure of DOPT.…”

Synthesis of carbon nanofibers by thermal conversion of the molecular precursor 5,6;11,12-di-o-phenylenetetracene and its application in a chemiresistive gas sensor

“…22 Saturated solutions of DOPT in dichloromethane (DCM) were prepared by dissolving 2 mg DOPT in 10 mL DCM. Needle-like crystals were deposited on individual substrates by simple drop coating of the as-prepared solution (Fig.…”

“…21 Herein, we demonstrate synthesis, characterization and sensoric behaviour of carbon nanobers with an amorphous structure (a-CNFs) by thermal conversion of the recently available cross conjugated tetracene molecule 5,6;11,12-di-ophenylenetetracene (DOPT, 3). 22, 23 The obtained a-CNFs were studied towards their functional properties in a chemiresistor device for the detection of toxic gases. For this, nitrogen dioxide, ammonia and sulfur dioxide were chosen as analyte gases.…”