Yusuke Ishigaki

Octaaryl-substituted bisquinodimethanes (BQDs) with a zigzag structure were designed as redox-switchable molecules that undergo four-electron oxidation to produce tetracationic pentacenes with a doubly twisted structure. In contrast to one-stage four-electron oxidation of BQDs, stepwise two-electron reduction of tetracationic pentacenes occurs to give dicationic anthracenes and then the original BQDs, step-by-step. Since both tetracations and dications exhibit near-infrared (NIR) absorptions (-1

Abstract Tetraarylanthraquinodimethane derivatives 1 with butterfly-shaped folded structures and the corresponding dications 12+ with twisted conformations can undergo interconversion upon two-electron transfer, which is accompanied by a drastic color change. While reversible electrochromic behavior occurs in solution, electron donors 1 exhibit fluorescence only in the solid state. The emission color changed upon grinding as-synthesized samples of 1, and the original emission color was recovered

Quinodimethanes (QDs) are a class of non-aromatic π-conjugated compounds that are well-known to be interconvertible scaffolds in many response systems. While parent ortho- and para-QDs (o-QD and p-QD) can be easily converted to benzocyclobutenes or oligomers/polymers by the formation of C-C bonds at α-positions, the attachment of four phenyl groups to these reactive sites makes o-Ph₄QD and p-Ph₄QD long-lived. We have demonstrated that further dibenzo-annulation of such tetr

A series of six dications composed of pure hydrocarbons with one to six non-substituted 9,10-anthrylene units end-capped with two dibenzotropyliums were designed and synthesized to elucidate the electronic properties of huge oligo(9,10-anthrylene) backbones. Their structures were successfully determined by X-ray analyses even in the case of eight planar 14π-electron units, revealing that all dications adopt almost orthogonally twisted structures between neighboring units. Spectroscopic and volta

Tetraazaanthraquinodimethanes can exhibit various colours and emissions depending on their multiple conformations, such as not only folded and twisted forms but also intermediate structures, e.g. , planar and twisted-folded forms, in pseudopolymorphs.

The title dispiro hydrocarbon 1 was designed as a new electrochromic material. This multiply clamped hexaphenylethane-type electron donor was prepared from 2,2'-diiodobiphenyl via biphenyl-2,2'-diylbis(dibenzotropylium) 2²⁺ salt. X-ray analysis of 1 revealed a highly strained structure as reflected by an elongated "ethane" bond [bond length: 1.6665(17) Å] and nearly eclipsed conformation. The weakened bond was cleaved upon two-electron oxidation to regenerate the deeply colored dicati

Abstract In the crystals of 4,7-dihalobenzo[c][1,2,5]chalcogenadiazoles, the molecules are connected by two competing secondary bonding interactions: chalcogen bond (ChB) and halogen bond (HaB). Because the strengths of ChB and HaB change according to the kind of chalcogen (E: S, Se, Te) and halogen (X: Cl, Br, I), their relative contributions in determining the crystal packing can also change. Six newly determined crystal structures as well as 3 previously reported structures can be categorized

Abstract The title nonplanar electron acceptor ( 1 ) fused with a selenadiazole ring selectively forms a crystalline charge‐transfer complex (CT crystal) with 2,6‐dimethylnaphthalene (2,6‐DMN). On the other hand, the sulfur analogue ( 2 ) has less recognition ability and forms CT crystals with both 2,6‐ and 2,7‐DMN. X‐ray analyses of 1 , 2 , and their CT crystals revealed that the Se⋅⋅⋅N chalcogen bond (ChB) in 1 is strong enough to determine the crystal packing with the formation of a cavity su

A series of biphenyl-2,2'-diylbis(diarylmethanol)s 3, which have two kinds of aryl groups at the bay region, were efficiently obtained by integrated flow microreactor synthesis. The diols 3NO/NX are the precursors of unsymmetric biphenylic dications 2NO/NX²⁺, which are transformed into the corresponding dihydrophenanthrenes 1NO/NX via 2NO/NX^+• upon reduction, when they exhibit two-stage color changes. On the other hand, the steady-state concentration of the intermediate 2NO

When the 1,1,4,4-tetraanilinobutadiene skeleton is attached with two halogenated aryl units at the 2,3-positions, they undergo facile two-electron oxidation to give stable dicationic dyes which exhibit a near-infrared (NIR) absorption whereas the neutral dienes show only pale color. Therefore, a distinct electrochromic response with an absorption change in the NIR region is achieved, which is attracting considerable recent attention from the viewpoint of bioimaging. Herein, we demonstrate that t

A nitrogen-centered heptalene, azaheptalene, was designed as a representative of a new class of redox-responsive molecules with a large steric strain that originates from the adjacent seven-membered rings. The pentabenzo derivative of azaheptalene was efficiently synthesized by a palladium-catalyzed one-pot reaction of commercially available reagents. Bromination led to mono- and dibrominated derivatives, the latter of which is interconvertible with isolable radical cation species exhibiting nea

Organic chemistry has developed rapidly as a carbon-based science. Particularly, hydrocarbons with aromatic rings have attracted much attention as molecular materials for use in organic electronics. In principle, aromatic species can be constructed if carbon and hydrogen atoms are available. Therefore, revealing the nature of pure hydrocarbons with an (anti)aromatic nature should pave the way for the development of as yet unexplored organic materials. In this Review, we focus on pure hydrocarbon

Abstract Molecules with an extreme structural parameter, such as an elongated C-C bond, have attracted much attention due to their special properties, which ordinary molecules do not have. Stabilized hexaphenylethanes are suitable compounds for seeking for the longest C-C bond. In addition to steric repulsion among the aryl groups (“front strain”) found in 1,1,2,2-tetraarylacenaphthenes (1), “scissor effects” cause expansion of the C1-C2 bond in 1,1,2,2-tetraarylpyracenes (2). A series of crysta

Electrochromic systems capable of switching absorption in the near-infrared (NIR) region (750-2500 nm) are attractive from the viewpoint of applications for material and life science, and thus several examples have been reported to date. In general, the development of organic-based systems is needed to reduce the environmental impact and improve biocompatibility. Although extending the switchable spectral range is crucial for the application of organic electrochromic molecules, the switching of

Electrochromic systems capable of switching near-infrared (NIR) absorption are fascinating from the viewpoint of applications in the materials and life sciences. Although 11,11,12,12-tetraaryl-9,10-anthraquinodimethanes (AQDs) with a folded form undergo one-stage two-electron oxidation to produce twisted dicationic dyes exhibiting NIR absorption, there is a need to establish a design strategy that can enhance the NIR-absorbing abilities of the corresponding dicationic dyes. In this study, we des