Yasutomo Segawa

Activation of aromatic CH bonds by a transition metal catalyst has received significant attention in the synthetic chemistry community. In recent years, rapid and site-selective extension of π-electron systems by C-H activation has emerged as an ideal methodology for preparing organic materials with extended π-systems. This Review focuses on recently reported π-extending C-H activation reactions directed toward new optoelectronic conjugated materials.

The synthesis of a carbon nanobelt, comprising a closed loop of fully fused edge-sharing benzene rings, has been an elusive goal in organic chemistry for more than 60 years. Here we report the synthesis of one such compound through iterative Wittig reactions followed by a nickel-mediated aryl-aryl coupling reaction. The cylindrical shape of its belt structure was confirmed by x-ray crystallography, and its fundamental optoelectronic properties were elucidated by ultraviolet-visible absorption, f

Nucleophilic, anionic boryl compounds are long-sought but elusive species. We report that reductive cleavage of the boron-bromine bond in N,N'-bis(2,6-diisopropylphenyl)-2-bromo-2,3-dihydro-1H-1,3,2-diazaborole by lithium naphthalenide afforded the corresponding boryllithium, which is isoelectronic with an N-heterocyclic carbene. The structure of the boryllithium determined by x-ray crystallography was consistent with sp(2) boron hybridization and revealed a boron-lithium bond length of 2.291 +/

The selective and predictable synthesis of structurally uniform carbon nanotubes (CNTs) represents a long-standing goal in both nanocarbon science and synthetic organic chemistry. This Review focuses on synthetic studies toward the controlled synthesis of CNTs with single chirality through the organic synthesis of CNT segments and the organic template assisted growth of CNTs.

A series of lithium salts of boryl anion, boryllithiums, were synthesized and characterized by NMR spectroscopy and crystallographic analysis. In addition to the parent boryllithium compound 35a, structural modification of boryllithium, using saturated C-C and benzannulated C=C backbones in the five-membered ring and mesityl groups on the nitrogen atoms, also allowed generation of the corresponding boryllithium. The solid state structures of boryllithium showed that the boron-lithium bond is pol

We studied the UV-vis absorption and fluorescence in solution/solid states of [n]cycloparaphenylene ([n]CPP: n = 9, 12, 14, 15, and 16), and conducted theoretical studies to better understand the experimental results. The representative experimental findings include (i) the most intense absorption maxima (λ(abs1)) display remarkably close values (338-339 nm), (ii) the longest-wavelength absorption maxima (λ(abs2)) are blue-shifted with increasing the ring size (395 → 365 nm), (iii) the emission

The generation of topologically complex nanocarbons can spur developments in science and technology. However, conventional synthetic routes to interlocked molecules require heteroatoms. We report the synthesis of catenanes and a molecular trefoil knot consisting solely of <i>para</i>-connected benzene rings. Characteristic fluorescence of a heterocatenane associated with fast energy transfer between two rings was observed, and the topological chirality of the all-benzene knot was confirmed by en

The structures and strain energies of cycloparaphenylenes (CPPs) have been determined by DFT calculation at the B3LYP/6-31G(d) level of theory. Fifteen stable conformations of [12]CPP were found as local minimum structures. It was also found that benzene rings of [12]CPP can rotate rather freely at room temperature. The strain energies of [n]CPP (n = 6-20) were estimated on the basis of the homodesmotic reaction using CPP, biphenyl, and p-terphenyl. It was also found that CPPs have higher strain

High quality ZnO thin film was grown by Laser MBE. A pure ceramic ZnO target was ablated by the KrF laser pulses (248 nm, 10 Hz, 1 J/cm2) in an ultra high vacuum to deposit ZnO film on sapphire (0001) substrate. The lateral grain size was about 50 nm for the sample with thickness of 55 nm. At room temperature, the peak of the exciton absorption and the photoluminescence have the same energy. Under high density excitation (355 nm, 35 ps, 10 Hz), an exciton–exciton collision process was observed a

Crystal clear: The title macrocycle was constructed by a nickel-mediated shotgun macrocyclization. The X-ray crystallographic structure of [12]CPP revealed a circular structure incorporating two cyclohexane molecules within the ring. The [12]CPP molecules were also found to crystallize into tubular and herringbone structures.

We synthesized a PBP pincer ligand precursor 2 and demonstrated its complexation with iridium(I) to afford the coordinatively unsaturated [PBP](hydrido)chloroiridium complex 3 via B-H oxidative addition. The reaction of 3 with carbon monoxide produced [PBP](hydrido)chloro(carbonyl)iridium 7. The longer Ir-Cl bond length of 7 than that of 8 revealed a stronger sigma-donor ability of the PBP ligand than that of PCP. Complex 3 was also converted to [PBP](ethylene)iridium(I) complex 9 by the reactio

Nucleophilic borylation: Transmetalation from boryllithium compounds to Group 11 transition-metal chlorides gives the corresponding boryl complexes (see scheme). Borylsilver and borylgold complexes that have three-center-two-electron MB bonds are fully characterized for the first time. The NMR spectra and solid-state structures of the resulting boryl complexes reveal that the boryl ligand is one of the strongest known σ-donor ligands. Supporting information for this article is available on the

Abstract Die Aktivierung von aromatischen C‐H‐Bindungen durch einen Übergangsmetallkatalysator ist ein wichtiges Thema in der Synthesechemie. In den letzten Jahren hat sich die schnelle und regiospezifische Erweiterung von π‐Systemen durch C‐H‐Aktivierung zu einer idealen Methode zur Herstellung von organischen Materialien mit ausgedehntem π‐System entwickelt. Dieser Aufsatz fasst neuere Reaktionen zur C‐H‐Aktivierung für die Erweiterung von π‐Systemen im Hinblick auf neue optoelektronische konj

The synthesis and X-ray crystal structure of the first member of the carbon nanobelt family is reported. [12]Carbon nanobelt ([12]CNB) was originally obtained from a nickel-mediated reductive coupling reaction of a dodecabrominated macrocyclic precursor, albeit only in 1% yield. The present article reports on the development of this synthetic strategy and its extension to the preparation of the [16] and [24]CNB analogues. In particular, our extensive investigations on the final belt-forming, nic