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      From open-shell singlet diradicaloids to polyradicaloids

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          Abstract

          We highlight our recent studies on stable open-shell singlet diradicaloids and polyradicaloids, originating from Chichibabin's hydrocarbon reported 110 years ago.

          Abstract

          In this Feature Article, we highlight our recent efforts toward stable open-shell singlet diradicaloids and polyradicaloids. A brief review on the historical works in the area is introduced first, followed by discussion on the fundamental electronic and physical properties of open-shell singlet diradicaloids. Then, the structure–diradical character relationships based on our recently developed diradicaloids are presented. Next, the challenges and solutions toward stable polyradicaloids and 3D π-conjugated diradicaloids are discussed. Finally, their preliminary material applications are introduced and a perspective view of the area is given.

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          Edge state in graphene ribbons: Nanometer size effect and edge shape dependence

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            Singlet fission.

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              Electronic structure and stability of semiconducting graphene nanoribbons.

              We present a systematic density functional theory study of the electronic properties, optical spectra, and relative thermodynamic stability of semiconducting graphene nanoribbons. We consider ribbons with different edge nature including bare and hydrogen-terminated ribbons, several crystallographic orientations, and widths up to 3 nm. Our results can be extrapolated to wider ribbons providing a qualitative way of determining the electronic properties of ribbons with widths of practical significance. We predict that in order to produce materials with band gaps similar to Ge or InN, the width of the ribbons must be between 2 and 3 nm. If larger bang gap ribbons are needed (like Si, InP, or GaAs), their width must be reduced to 1-2 nm. According to the extrapolated inverse power law obtained in this work, armchair carbon nanoribbons of widths larger than 8 nm will present a maximum band gap of 0.3 eV, while for ribbons with a width of 80 nm the maximum possible band gap is 0.05 eV. For chiral nanoribbons the band gap oscillations rapidly vanish as a function of the chiral angle indicating that a careful design of their crystallographic nature is an essential ingredient for controlling their electronic properties. Optical excitations show important differences between ribbons with and without hydrogen termination and are found to be sensitive to the carbon nanoribbon width. This should provide a practical way of revealing information on their size and the nature of their edges.
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                Author and article information

                Journal
                CHCOFS
                Chemical Communications
                Chem. Commun.
                Royal Society of Chemistry (RSC)
                1359-7345
                1364-548X
                2018
                2018
                : 54
                : 18
                : 2186-2199
                Affiliations
                [1 ]Department of Chemistry
                [2 ]National University of Singapore
                [3 ]Singapore
                Article
                10.1039/C7CC09949E
                d6b8f276-85ce-4d42-b071-e2a7cbd936c8
                © 2018

                http://rsc.li/journals-terms-of-use

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