La fundación de la Madrasa al-Adāb por la Asociación de ulemas musulmanes argelinos en la ciudad de Hennaya (Tremecén) en 1950

A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the β-position of the BODIPY unit. The extended π-system of the fused BODIPY induces near-infrared (NIR) absorption and strong π–π interactions in the solid state. These features are beneficial for the application of the dye as a functional material. The biphenyl-fused BODIPY dye was demonstrated to exhibit photocurrent conversion ability on the basis of its <i>n</i>-type semiconducting property

Synthesis and Properties of <i>meso</i>-Arylated Corrphycenes

A novel synthetic procedure for <i>meso</i>-aryl-substituted corrphycenes has been developed. Suzuki–Miyaura coupling of α,α′-dibromodipyrrin with <i>vic</i>-diborylalkene and <i>o</i>-diborylbenzene afforded ethenylene- and phenylene-bridged bisdipyrrins, respectively, which were transformed to the corresponding corrphycenes upon treatment with palladium acetate. The bridging units significantly affect the macrocyclic π-conjugation circuits, thus changing the aromatic characters and absorption features of corrphycenes

What's the Story?

A review of the CD box set To the Outside of Everything: A story of Post-Punk 1977-1981 (Cherry Red)

Synthesis of Diazo-Bridged BODIPY Dimer and Tetramer by Oxidative Coupling of β‑Amino-Substituted BODIPYs

A diazo-bridged BODIPY dimer and tetramer were prepared by the oxidative coupling reaction of β-amino-substituted BODIPYs. The structure of the dimer was elucidated by X-ray diffraction analysis, showing its coplanar orientation of two BODIPY units. Effective extension of π-conjugation was confirmed by optical and electrochemical investigations

Synthesis of Free-Base 10-Azacorroles

A novel synthetic protocol has been developed for free-base 10-azacorroles. Ni(0)-mediated homocoupling of nitrogen-bridged bisdipyrrin Zn­(II) complexes afforded a series of free-base 5,15-diaryl-10-azacorroles in good yields. Pd­(II) and Cu­(II) complexes have been prepared through metalation of free-base 10-azacorroles. Optical and electrochemical properties of 10-azacorrole metal complexes can be tuned by <i>meso</i>-aryl substituents and central metals. Cyclic voltammetry and theoretical calculations elucidated that the central metals of 10-azacorroles significantly affected their electronic properties

Design and Synthesis of Tunable Ligands with 4,4′-Bipyridyl as an Electron-Accepting Unit and Their Rhenium Complexes

We have designed and prepared a series of rhenium complexes with 4,4′-bipyridyl as an electron-accepting unit. Electrochemical studies revealed that oxidation and reduction of these complexes occurred on the rhenium center and the 4,4′-bipyridyl skeleton, respectively. The redox potentials of the rhenium complexes are controllable by tuning the substituents on the 4,4′-bipyridyl skeleton and the coordinating groups to the rhenium center. We have also examined the reactivity of the rhenium complexes in electrochemical and photochemical CO₂ reduction

Acid-Mediated Migration of Bromide in an Antiaromatic Porphyrinoid: Preparation of Two Regioisomeric Ni(II) Bromonorcorroles

The regioselective halogenation of porphyrinoids is critical for their selective functionalization, which enables the fine tuning of their electronic and optical properties. Here we report the synthesis of two regioisomeric Ni­(II) bromonorcorroles on the basis of the acid-induced migration of the bromo substituent. Treatment of Ni­(II) dimesitylnorcorrole with <i>N</i>-bromosuccinimide (NBS) selectively afforded Ni­(II) 3-bromonorcorrole, which was further converted into Ni­(II) 2-bromonorcorrole upon treatment with hydrogen bromide. In addition, the reaction of Ni­(II) dimesitylnorcorrole with an excess amount of NBS afforded the octabrominated product. The reaction mechanism of the bromination reaction of Ni­(II) dimesitylnorcorrole was investigated by theoretical calculations

Synthesis of Oxygen-Substituted Hexa-<i>peri</i>-hexabenzocoronenes through Ir-Catalyzed Direct Borylation

Direct C–H borylation of hexa-<i>peri</i>-hexabenzocoronenes (HBCs) has been achieved under iridium catalysis, which allows efficient synthesis of hydroxy-substituted HBCs by oxidation of the boryl groups. Further oxidation of dihydroxy HBC with phenyliodine bis(trifluoroacetate) (PIFA) afforded tetraoxo-substituted HBC without any regioisomers, which can be considered as a π-extended quinone

Acid-Mediated Migration of Bromide in an Antiaromatic Porphyrinoid: Preparation of Two Regioisomeric Ni(II) Bromonorcorroles

The regioselective halogenation of porphyrinoids is critical for their selective functionalization, which enables the fine tuning of their electronic and optical properties. Here we report the synthesis of two regioisomeric Ni­(II) bromonorcorroles on the basis of the acid-induced migration of the bromo substituent. Treatment of Ni­(II) dimesitylnorcorrole with <i>N</i>-bromosuccinimide (NBS) selectively afforded Ni­(II) 3-bromonorcorrole, which was further converted into Ni­(II) 2-bromonorcorrole upon treatment with hydrogen bromide. In addition, the reaction of Ni­(II) dimesitylnorcorrole with an excess amount of NBS afforded the octabrominated product. The reaction mechanism of the bromination reaction of Ni­(II) dimesitylnorcorrole was investigated by theoretical calculations

Reversible σ‑Bond Formation in Bowl-Shaped π‑Radical Cations: The Effects of Curved and Planar Structures

The reversible formation of σ-bonds between organic radicals has been widely investigated. However, reports on the formation of σ-dimers from delocalized π-radical cations are scarce. Herein, we report the reversible σ-dimerization behavior of a bowl-shaped π-radical cation generated from a nitrogen-embedded buckybowl, both in the crystalline state and in solution. The detailed structure of the σ-dimer in the crystalline state was determined by a single-crystal X-ray diffraction analysis. The monomeric radical cation exists predominantly in solution at room temperature, while dimerization of the radical cations occurs through carbon–carbon σ-bond formation upon reducing the temperature. ¹H NMR and optical spectroscopy measurements confirmed the formation of a σ-dimer at low temperature. Comparative studies with a similar yet planar π-conjugated system suggested that the curved structure of the bowl-shaped π-radical cation facilitates the σ-dimerization at one of the internal sp²-hybridized carbon atoms. This trend was also observed for the nucleophilic addition reaction of methanol to the π-radical cations. The methoxylation reaction proceeded only for the curved π-radical cation. Theoretical calculations revealed that the large relief of structural strain at the α-carbon atom during the dimerization or nucleophilic addition reactions accelerated the bond formation at the internal carbon atom of the curved radical cation