Bottom-Up Synthesis of Twisted Porous Graphene through a Heterogeneous Scholl Reaction and Its Supercapacitor Application.

Anthracene- and pyrene-based twisted porous graphene (AN-Pyre-PG) with an ordered pore structure has been synthesized through bottom-up solution phase synthesis from a conjugated microporous polymer (AN-Pyre-CMP) via a heterogeneous Scholl cyclization reaction. The regular-ordered pores embedded within the graphene structures were analyzed through a Raman spectrum, different morphological analyses, and theoretical studies. A significant change in surface area from AN-Pyre-CMP to AN-Pyre-PG was observed, from 143 to 640 m2/g, respectively. Surface area-driven capacitive properties were also observed. Twisted-structure and ordered porous graphene shows better specific capacitance compared to CMP. AN-Pyre-PG shows a specific capacitance of 629 F g-1 at 1 A g-1, with 91% retention of capacitance after 3000 charge-discharge cycles, whereas AN-Pyre-CMP shows a maximum specific capacitance of 200 F g-1 was observed at 2 A g-1.

Diastereoselective Spirocyclization of Benzoxazines with Nitroalkenes via Rhodium-Catalyzed C-H Functionalization/Annulation Cascade under Mild Conditions.

A Rh(III)-catalyzed [3 + 2] annulation of benzoxazines with nitroolefins that proceeds via redox-neutral C-H functionalization has been demonstrated, leading to the novel class of spirocycles in a single step. The construction of three continuous stereogenic centers has been achieved starting from easily accessible achiral substrates in an atom-efficient manner under mild reaction conditions. A broad range of pharmaceutically relevant nitro substituted spirocyclic 2,3-dihydro-1,4-benzoxazine derivatives has been synthesized in good to excellent yields with high diastereoselectivity.

An interplay of cooperativity between cation⋠⋠⋠π, anion⋠⋠⋠π and C-H⋠⋠⋠anion interactions.

Mixed cation (Li(+), Na(+) and K(+)) and anion (F(-), Cl(-), Br(-)) complexes of the aromatic π-surfaces (top and bottom) are studied by using dispersion-corrected density functional theory. The selectivity of the aromatic surface to interact with a cation or an anion can be tuned and even reversed by the electron-donating/electron-accepting nature of the side groups. The presence of a methyl group in the -OCH3, -SCH3, -OC2H5 in the side groups of the aromatic ring leads to further cooperative stabilization of the otherwise unstable/weakly stable anion⋅⋅⋅π complexes by bending of the side groups towards the anion to facilitate C-H⋅⋅⋅anion interactions. The cooperativity among the interactions is found to be as large as 100 kcal mol(-1) quantified by dissection of the three individual forces from the total interaction energy. The crystal structures of the fluoride binding tripodal and hexapodal ligands provide experimental evidence for such cooperative interactions.