Liliia Moshniaha

Indene-annulated perylenes merge cyclopentadiene-like benzylic acidity with the multielectron redox chemistry of rylene carbonyl scaffolds, creating discrete redox–protonation (“Pourbaix”) spaces in which electron transfer and acid–base processes become intrinsically coupled. Here we map the accessible states of doubly and singly pentannulated perylenediimides and perylene tetraesters using absorption/emission spectroscopy, electrochemistry and spectroelectrochemistry, and DFT analysis.

Voltammograms of all derivatives show two quasi-reversible, largely core-centered reductions, yet the pentannulated tetraesters uniquely undergo electrochemically induced γ-deprotonation prior to core reduction, consistent with electrogenerated-base chemistry. Chemical stimulation reveals pronounced chemodivergence: potassium tert-butoxide readily produces deprotonated “dienolate” NIR chromophores in the pentannulated tetraester series, whereas the corresponding diimides first form perylene-centered radical anions/dianions that evolve into benzylic anions and higher multianions in a cation-dependent manner, with crown ether sequestering K+ and reshaping reaction trajectories.

Strong reductants enable entry into highly reduced charge states, including an X-ray-verified salt of a pentannulated diimide trianion displaying diverse potassium binding motifs, underscoring the non-innocent role of ion pairing. Oxidation of deprotonated dianions furnishes weakly coupled neutral diradicaloids with NIR absorption. These results establish indene-annulated rylenes as multistate NIR chromophores whose experimentally accessible Pourbaix subsets can be programmed by redox bias, base strength, and cation coordination, with direct implications for organic electrochromism and rylene-based energy-storage chemistries.

Boomerang-shaped bipyrroles containing donor–acceptor units were obtained through a tandem palladium-mediated reaction consisting of a cyclization step, involving double C–H bond activation, and a double α-oxygenation. The latter reaction can be partly suppressed for the least reactive systems, providing access to α-unsubstituted boomerangs for the first time. These “α-free” systems are highly efficient fluorophores, with emission quantum yields exceeding 80% in toluene. Preliminary measurements show that helicene-like boomerangs may be usable as circularly polarized luminescent materials.

A 139-π-electron nanographenoid radical was obtained by expanding the periphery of a naphthalimide–azacoronene hybrid with a methine bridge. The radical was isolated in the form of its σ-dimer, which was shown to possess a conformationally restricted two-layer structure both in the solid state and in solution. The dimer is cleaved into its parent radicals when exposed to ultraviolet or visible radiation in toluene solutions but is resistant to thermally induced dissociation. Under inert conditions, the radicals recombine quantitatively into the σ-dimer with observable kinetics, but they are oxidized into a ketone derivative in the presence of atmospheric oxygen. Combined structural, spectroscopic, and theoretical evidence shows that the σ-dimer contains a weak C(sp3)–C(sp3) bond, but is stabilized against thermal dissociation by a very strong dispersive interaction between the overlapping π surfaces.

1,n-Dipyrrolylalkanes can be efficiently converted into extensively π-conjugated bipyrroles by Pd^II-mediated annulative double C–H activation, and this approach might be further developed into tandem processes involving further cyclization of substituents or oxygenation of pyrrolic α-positions. Herein, the mechanism of these transformations is explored using NMR spectroscopy and DFT calculations. The kinetics of the annulation are found to depend on the conjugation extent and donor–acceptor character of the pyrroles, as well as on substitution and the linker length. Combined experimental and theoretical evidence indicates that a change of the rate-determining step occurs for the most electron-deficient substrates. The unprecedented double α-oxygenation of bipyrroles is found to be a stepwise process, involving α-acetoxylated intermediates.

Pd^II-mediated annulative double C−H activation is shown to efficiently convert 1,n-dipyrrolylalkanes into extensively π-conjugated bipyrroles not accessible by conventional oxidative coupling protocols. This approach is applicable to both electron-rich and electron-deficient systems, and has been further developed into tandem processes involving further cyclization of substituents or oxygenation of pyrrolic α-positions. The new bipyrrole intermediates show enhanced fluorescence as well as tunable optical properties controlled by the alignment of chromophore subunits. Photophysical data, including femtosecond transient absorptions, reveal solvent-induced intramolecular charge transfer in their excited states, dependent on the polarity of the medium.