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
The molecular structure of the hydrocarbon 5,6;11,12-di-o-phenylenetetracene (DOPT), its material characterization and evaluation of electronic properties is reported for the first time.Asingle-crystal X-rays tudy reveals two different motifs of intramolecular overlap with herringbonetype arrangement displaying either face-to-edge or co-facial face-to-face packing depicting intensive p-p interactions. Density functional theory (DFT) calculations underpin that afavorable electronic transport mechanism occurs by acharge hopping process due to a p-bond overlap in the DOPT polymorph with co-facial arene orientation. The performance of polycrystalline DOPT films as active organic semiconducting layer in as tate-of-the-art organic field effect transistor (OFET) device was evaluated and proves to be film thickness dependent. For4 0nml ayer thickness it displays as aturation hole mobility (m hole)o fu pt o0 .01 cm 2 V À1 s À1 and an on/offratio (I on /I off)o f1.5 10 3 .
Herein, we report the synthesis and molecular structure of the mono- and dianionic aromatic molecules [(B15C5-κ5O)2K+](LDOPT˙-) (1) and [(B15C5-κ5O)2K+]2(LDOPT2-)THFsolv (2) derived from the parent aromatic polyhydrocarbon 5,6:11,12-di-o-phenylenetetracene (DOPT, LDOPT) by a controlled stepwise one and two electron chemical reduction. The effect of single and double electron charge transfer to a polycondensed aromatic hydrocarbon (PAH) without any disturbing influence of an associated metal cation has been demonstrated. This was achieved by fully sandwiching the cationic K+ counterions between two benzo-15-crown-5-ether (B15C5) ligands resulting in a fully encapsulating (κ10O) geometry which ensures a complete separation of the K+ counterions and the bare anionic PAH species [LDOPT˙-] and [LDOPT2-]. The structural changes accompanied by the stepwise reduction from LDOPT to [LDOPT˙-] to [LDOPT2-] are discussed and compared to earlier predictions based on density functional theory (DFT) as well as the results of previous studies of alkaline metal cationic PAH anion interactions of DOPT in which only a partial metal cation encapsulation has been achieved so far.
Twofold reduction of the title molecule 5,6;11,12-di-o-phenylenetetracene (DOPT) with an excess of metallic rubidium and cesium in the presence of strongly coordinating ethers like 18-crown-6-ether (18C6) and tetraglyme results in the formation of the first Rb(i) triple-decker complex and the first Cs(i) coordination polymer of the so far only sparsely studied polyaromatic planar hydrocarbon DOPT. Both compounds are extremely sensitive towards air and water in solution as well as in the solid state. Both compounds exhibit isomerism within their crystal lattices.
Herein we report the synthesis and crystal structures of three light alkali metal salts of the dianion of the polycyclic aromatic hydrocarbon 5,6:11,12-di-o-phenylenetetracene (L). The compounds are obtained by reaction of L with an excess of lithium or sodium metal in different O-donor solvents (DME, diglyme) and crystallize as naked, solvated-cation separated dianions exhibiting no interaction between the alkali metal ion and the aromatic π-system of L. Depending on the aprotic etheral solvent and the hardness of the alkaline metal agent a significant structural perturbation of the conjugated carbon framework of L is observed resulting in a bowl shaped curvature of the anionic π-perimeter, in contrast to its fully planar neutral state. Reduction of L with lithium in DME results in the formation of the solvent-separated molecular structure of {[(DME-κO)Li](L)}1 containing naked isolated units of dianionic L. A similar structural arrangement is observed for the corresponding sodium compound {[(DME-κO)Na](L)}2 in which, however, a lesser curvature of the isolated dianionic ligand skeleton compared to 1 is observed. In contrast to 1 and 2 reduction with sodium in diglyme results in the formation of {[(diglyme-κO)Na](L)}3. The deformation of the peripheric phenylene rings of [L] in 3 is not as pronounced as compared to 1 and 2. Nevertheless, molecular structures of 1-3 deviate from full-planarity as observed in the parent neutral L. No preferential endo- or exo-site coordination of the alkaline metal cations Li and Na on the curved dianionic π-perimeter is observed.
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