π-Extended 4,5-Fused Bis-Fluorene: Highly Open-Shell Compounds and their Cationic Tetrathiafulvalene Derivatives.

The synthesis of diradical organic compounds has garnered significant attention due to their thermally accessible spin inversion and optoelectronic properties. Yet, preparing such stable structures with high open-shell behavior remains challenging. Herein, we report the synthesis and properties of four π-extended, fused fluorene derivatives with high diradical character, taking advantage of a molecular design where the closed-shell does not include any Clar sextet, comparatively to a maximum of 5 in the corresponding open-shell state. This led to an unusual open-shell triplet ground state with an outstanding singlet-triplet energy difference (ΔEST) of ca. 19 kcal/mol, one of the highest values reported to date for an all-carbon conjugated scaffold. Incorporation of dithiafulvene units at each end of the molecule (at the five-membered rings) furnishes extended tetrathiafulvalenes (TTFs) undergoing reversible oxidations to the radical cation and diradical dication. The various pro-aromatic structures presented herein show highly localized spin density and a limited conjugation due to the confined π-electrons in the aromatic cycles, as supported by 1H NMR, UV-visible, EPR spectroscopy and DFT calculations.

Spatiotemporal variability in diet composition of Greenland halibut (Reinhardtius hippoglossoides) from the eastern Canadian Arctic.

Greenland halibut (Reinhardtius hippoglossoides) sustain one of the most lucrative fisheries in the eastern Canadian Arctic and Labrador Sea. This species also plays an important role in food web connectivity and benthic-pelagic coupling. Despite the relatively rich knowledge of this species, R. hippoglossoides ecology in these specific areas remains poorly understood. The main aim of this study was to characterize the diet of this deepwater fish in the Labrador Sea and Davis and Hudson Straits and characterize the predator-prey relationship with northern shrimp (Pandalus borealis), another commercially important species in the region. Stomach contents analyses were conducted on 1199 fish captured from 2018 to 2020. Small specimens (<20 cm) fed on invertebrates, whereas larger individuals (>60 cm) fed primarily on fish, indicative of size-related changes in diet composition. The relative abundance of Pandalus shrimp species in the environment was reflected in the diet. Location appeared to be the most influential variable on feeding patterns. Distinct oceanographic conditions among areas, resulting in differences in prey availability, could explain these results. Arctic cod (Boreogadus saida) and redfish (Sebastes sp.) were selected in locations where fish prey were the most abundant. These results shed light on the opportunistic nature of R. hippoglossoides and its preference for fish at large size. With the rapidly changing oceanographic conditions of Arctic waters, a distributional change in the biomass of shrimp is expected. Results suggest that an increase in abundance of predatory groundfish species in the system (e.g., Sebastes sp.) could lead to acute predation on shrimp and competition with R. hippoglossoides. By revealing key trophic links within the demersal ecosystem, this work provides valuable information on the development of ecosystem approaches to fisheries management for the region.

Pyrrole-Embedded Linear and Helical Graphene Nanoribbons.

Linear and helical graphene nanoribbons (L-PyGNR and H-PyGNR) bearing electron-rich pyrrole units have been synthesized by using the photochemical cyclodehydrochlorination (CDHC) reaction. The pyrrole units in the polymer backbone make the polymer electron-rich with moderate bandgap values and relatively high HOMO energy levels. The planarization of the pyrrole unit through cyclization yields a bandgap value almost 0.5 eV lower than that measured for polypyrrole. Conductivity values in the thin film up to 0.12 S/cm were measured for the chemically oxidized L-PyGNR (four-point method). Both GNRs showed excellent fluorescence sensing properties for TNT in solution with KSV values up to 6.4 × 106 M-1.