π-dimerization of pleiadiene radical cations at low temperatures revealed by UV–vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[ c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293–263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPRsilent π-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; logεmax=4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF6 − salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol−1 (DFT B3LYP) [37.64 kcal mol−1 (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TDDFT- calculated UV–vis spectra of the PF6 − salt of the pleiadiene dimer dication, considering solvent (THF) effects.

Non-cinema: the location of politics in film

Philosophy has repeatedly denied cinema in order to grant it artistic status. Adorno, for example, defined an ‘uncinematic’ element in the negation of movement in modern cinema, ‘which constitutes its artistic character’. Similarly, Lyotard defended an ‘acinema’, which rather than selecting and excluding movements through editing, accepts what is ‘fortuitous, dirty, confused, unclear, poorly framed, overexposed’. In his Handbook of Inaesthetics, Badiou embraces a similar idea, by describing cinema as an ‘impure circulation’ that incorporates the other arts. Resonating with Bazin and his defence of ‘impure cinema’, that is, of cinema’s interbreeding with other arts, Badiou seems to agree with him also in identifying the uncinematic as the location of the Real. This article will investigate the particular impurities of cinema that drive it beyond the specificities of the medium and into the realm of the other arts and the reality of life itself. Privileged examples will be drawn from various moments in film history and geography, starting with the analysis of two films by Jafar Panahi: This Is Not a Film (In film nist, 2011), whose anti-cinema stance in announced in its own title; and The Mirror (Aineh, 1997), another relentless exercise in self-negation. It goes on to examine Kenji Mizoguchi’s deconstruction of cinematic acting in his exploration of the geidomono genre (films about theatre actors) in The Story of the Last Chrysanthemums (Zangigku monogatari, 1939), and culminates in the conjuring of the physical experience of death through the systematic demolition of film genres in The Act of Killing (Joshua Oppenheimer et al., 2012).