Kyuya Yakushi

We present the results of tight-binding band-structure calculations on a deformable polypyrrole chain, as a function of doping. The states which are produced are polarons and bipolarons whose excitation spectrum explains the optical-absorption data.

A phenalenyl-based Kekulé hydrocarbon with singlet biradical character has been isolated and characterized. Strong intra- and intermolecular interactions between the unpaired electrons lead to short π–π contacts and formation of one-dimensional chains (see picture). Thus, wide valence and conduction bands are established, and the compound shows semiconductive behavior. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z502303_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

The optical transmittance spectra of polypyrrole perchlorate have been measured at various stages in the reduction to neutral polypyrrole at 300 and 120 K and at high pressure. Analysis of the results suggests that the polypyrrole chain is composed of conjugated segments of various lengths. The optical conductivity spectrum of polypyrrole perchlorate was obtained by the Kramers–Kronig transformation of the transmittance data from 0.025 to 6.25 eV. The spectrum is not consistent with Drude-like free carriers. The conduction mechanism probably involves hopping between the conjugated segments.

A novel naphthoquinoid singlet biradical (2a) stabilized by phenalenyl rings is prepared by a multistep procedure and is investigated in terms of covalent bonding interactions. The molecule 2a gives single crystals, in which a 1D chain is formed with a very short π-π contact at the overlapping phenalenyl rings. The unpaired electrons in 2a are involved in covalent bonding interactions not only within the molecule but also between the molecules in the 1D chain, and a linear conjugation is made of the alternating intra- and intermolecular covalent bonding interactions through conventional π-conjugation and multicenter bonding, respectively. The linear conjugation causes a lower-energy shift of the optical transition band in the crystal, but the transition energy is higher than that of the benzoquinoid singlet biradical (1a). This optical behavior and the magnetic susceptibility measurements reveal that the intermolecular covalent bonding interaction in the 1D chain of 2a is greater in strength than the intramolecular one, despite the fact that a fully conjugated Kekulé structure can be drawn for 2a.

Two flavors: Intra- and intermolecular spin–spin interactions of unpaired electrons coexist and correlate in stacks of phenalenyl-based singlet biradicals. The electronic structure of the one-dimensional π–π chain is best represented by the superposition of formulas A and B in terms of the resonating valence-bond (RVB) model. Lower temperatures and higher pressures induce a resonance balance shift to the formula B. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.