Supramolecular Porphyrin‐Based Metal–Organic Frameworks with Fullerenes: Crystal Structures and Preferential Intercalation of C70

The syntheses and characterization of two new porphyrin‐based metal–organic frameworks (P‐MOFs), through the complexation of 5,10,15,20‐tetra‐4‐pyridyl‐21 H,23 H‐porphine (H₂TPyP) and copper(II) acetate (CuAcO) in the presence of the fullerenes C₆₀ or C₇₀ are reported. Complex 1 was synthesized in conjunction with C₆₀, and this reaction produced a two‐dimensional (2D) porous structure with the composition CuAcO‐CuTPyP?m‐dichlorobenzene (m‐DCB), in which C₆₀ molecules were not intercalated. Complex 2 was synthesized in the presence of C₇₀, generating a three‐dimensional (3D) porous structure, in which C₇₀ was intercalated, with the composition CuAcO‐CuTPyP?C₇₀?m‐DCB?CHCl₃. The structures of these materials were determined by X‐ray diffraction to identify the supramolecular interactions that lead to 2D and 3D crystal packing motifs. When a combination of C₆₀ and C₇₀ was employed, C₇₀ was found to be preferentially intercalated between the porphyrins.     

Photoinduced Charge Separation of Polystyrene-Bound Ni[II], 4, 4, 4-Tetracarboxyphthalocyanine

Polystyrene with pendant Ni-(II)-4,4′, 4, 4 -tetracarboxyphthalocyanine (NiPctc) was synthesized by reacting NiPctc with partially chloromethylated polystyrene. Photoreduction of methylviologen by visible light was accomplished with the modified polymer. The photocatalytic activity was enhanced by bonding the NiPctc units to the polymer. The relationship between the catalytic activity and the structure of the modified polymer is discussed.     

New Preparation of α,β-Unsaturated Esters from 1-Alkenes Via Two Carbon Homologation Route. Synthesis of Queen Substance

2-Methylthio-4-alkenoic esters prepared from 1-alkenes and ethyl methylsulfinylacetate are converted into α,β-unsaturated esters via hydrogenation, oxidation, and thermolysis. This method was applied to the synthesis of queen substance.     

Asymmetric Dearomative Fluorination of 2-Naphthols with a Dicarboxylate Phase-Transfer Catalyst

A linked dicarboxylate phase-transfer catalyst enables smooth asymmetric dearomative fluorination of 2-naphthols with Selectfluor under mild conditions to give the corresponding 1-fluoronaphthalenone derivatives in a highly enantioselective manner. This reaction, which is compatible with a range of functional groups, is the first example of catalytic asymmetric fluorination of 2-naphthols, and is expected to be useful in the synthesis of bioactive molecules.     

Three New Resin Glycosides and a New Tetrahydropyran Derivative from the Seeds of <i>Quamoclit pennata</i>

Three new resin glycosides, quamoclins V (1), VI (2), and VII (3) and a new tetrahydropyran derivative, quamopyran (4), were isolated from the seeds of Quamoclit pennata BOJER (Convolvulaceae). The chemical structures of these compounds were determined primarily on the basis of spectroscopic data. The carboxyl group of the aglycone, 11S-convolvulinolic acid, of 1 and 2 was linked intermoleculary with a hydroxy group of the sugar moiety to form a macrocyclic ester structure, as in already known jalapins, and 3 was an acylated glycosidic acid methyl ester. All of the sugar moieties of 1-3 were acylated by one 2S-methylbutyric acid. Compound 4 was a diketone having a tetrahydropyran ring.     

Molecular structure and vibrational spectra of phenolphthalein and its dianion

Infrared (IR) and Raman spectra of phenolphthalein (PP) and its dianion form (sodium and potassium salts) were studied both in the solid state and in aqueous solution. Band assignments were carried out on the basis of the isotope shifts of the ring deuterated and 13C-substituted derivatives. Spectral analyses reveal that the PP dianion exists as mixtures of the benzenoid form (colorless) and the quinonoid form (colored) in the solid state and in aqueous solution, while the neutral PP solely takes the gamma-lactone form. This work provides the first vibrational spectroscopic evidence for the coexistence of the two species in the PP dianions.     

Statistical properties of weighted complex networks characterized by metaweights

We propose several characterizations of weighted complex networks by incorporating the concept of metaweight into the clustering coefficient, degree correlation, and module decomposition. These incorporations make it possible to describe weighted networks depending on how strongly we emphasize weights. Using some applications to real-world weighted networks, we demonstrate that the proposed approach provides rich information that was inaccessible by previous analyses such as the degree correlation for a specific magnitude of weights or the community structure under controlling the importance of roles of the topology and weights.