Anti-ohmic Nanoconductors: Myth, Reality and Promise

The recent accomplishments in the design of molecular nanowires characterised by an increasing conductance with length has embarked the origin of extraordinary new family of molecular junctions referred to as "anti-ohmic" wires. Herein, this highly desirable, non-classical behavior, has been examined for the longer enough molecules exhibiting pronounced diradical character in their ground state within the unrestricted DFT formalism with spin and spatial symmetry breaking. We demonstrate that highly conjugated acenes signals higher resistance in open-shell singlet (OSS) configuration as compared to their closed-shell counterparts. This anomaly has been further put to proof for experimentally certified cumulene wires, which reveals phenomenal modulation in the transport characteristics such that an increasing conductance is observed in closed-shell limit, while higher cumulenes in OSS ground state yields a regular decay of conductance.

Evolution of the electronic structure in open-shell donor-acceptor organic semiconductors

Most organic semiconductors have closed-shell electronic structures, however, studies have revealed open-shell character emanating from design paradigms such as narrowing the bandgap and controlling the quinoidal-aromatic resonance of the π-system. A fundamental challenge is understanding and identifying the molecular and electronic basis for the transition from a closed- to open-shell electronic structure and connecting the physicochemical properties with (opto)electronic functionality. Here, we report donor-acceptor organic semiconductors comprised of diketopyrrolopyrrole and naphthobisthiadiazole acceptors and various electron-rich donors commonly utilized in constructing high-performance organic semiconductors. Nuclear magnetic resonance, electron spin resonance, magnetic susceptibility measurements, single-crystal X-ray studies, and computational investigations connect the bandgap, π-extension, structural, and electronic features with the emergence of various degrees of diradical character. This work systematically demonstrates the widespread diradical character in the classical donor-acceptor organic semiconductors and provides distinctive insights into their ground state structure-property relationship.

The Interplay between Diradical Character and Stability in Organic Molecules

The number of scientific papers on the unique properties and the potential for various applications of compounds with a diradical character is growing constantly. The diradical character enhances and even engenders certain desired optical properties and its modulation is a modern molecular design strategy. Nowadays, molecules with a non-zero diradical character are regarded as promising materials for new-generation and highly efficient solar cells and photonics devices. What is the price, however, of the unique properties of open-shell compounds? Alongside all the benefits, the diradical character is usually associated with low stability and high reactivity—unwanted molecular qualities for practical purposes. Thus, from a fundamental and applied point of view, it is important to investigate the correlation between the diradical character and laboratory stability, which is the goal of the present paper. Here, we report a combined quantum–chemical study (conceptual DFT and spin-projected HF theory) and multivariate analysis of the diradical character of a series of o- and p-quinomethides, for the stability of which experimental data are available. Our results reveal that a compromise between the diradical character and laboratory stability of a molecule is feasible and that the relationship between these two quantities can be understood in the framework of Clar’s sextet theory.