Electronic Couplings for Triplet-Triplet Annihilation Upconversion in Crystal Rubrene.

Triplet-triplet annihilation photon upconversion (TTA-UC) is a process able to repackage two low-frequency photons into light of higher energy. This transformation is typically orchestrated by the electronic degrees of freedom within organic compounds possessing suitable singlet and triplet energies and electronic couplings. In this work, we propose a computational protocol for the assessment of electronic couplings crucial to TTA-UC in molecular materials and apply it to the study of crystal rubrene.

Synthesis of a Dicyclohepta[a,g]heptalene-Containing Polycyclic Conjugated Hydrocarbon and the Impact of Non-Alternant Topologies.

Incorporating non-hexagonal rings into polycyclic conjugated hydrocarbons (PCHs) can significantly affect their electronic and optoelectronic properties and chemical reactivities. Here, we report the first bottom-up synthesis of a dicyclohepta[a,g]heptalene-embedded PCH (1) with four continuous heptagons, which are arranged in a "Z" shape. Compared with its structural isomer bischrysene 1 R with only hexagonal rings, compound 1 presents a distinct antiaromatic character, especially the inner heptalene core, which possesses clear antiaromatic nature.

Benzene Excimer and Excited Multimers: Electronic Character, Interaction Nature, and Aromaticity.

In this Letter we analyze the forces involved in the formation of the benzene excimer and its electron structure, and (anti)aromatic character. We extend our study to excited states in molecular aggregates, the triplet excimer and the benzene-tricyanobenzene exciplex. Electronic wave functions are decomposed in terms of localized excitations and ion-pair configurations through diabatization, and we show that excimer (anti)aromaticity can be described as the linear combination of ground, excited, and ionic molecular states.

Intramolecular Palladium(II)-Catalyzed 6- C-H Alkenylation Directed by the Remote -Protecting Group: Mechanistic Insight and Application to the Synthesis of Dihydroquinolines.

A protocol for the Pd(II)-catalyzed C-H alkenylation reaction of substituted -allylanilines via an unusual 6- process has been developed. A density functional theory (DFT) study of the mechanistic pathway has shown that the coordination of the remote protecting group to the palladium center is determinant for the control of the regioselectivity in favor of the 6- process. The reaction would proceed via prior activation of the alkene.