Stacking Control by Molecular Symmetry of Sterically Protected Phthalocyanines

The synthesis and characterization of two phthalocyanine (Pc) structural isomers, 1 and 2, in which four 2,6-di(hexyloxy)phenyl units were attached directly to the 1,8,15,22- or 1,4,15,18-positions of the Pc rings, are described. Both Pcs 1 and 2 exhibited low melting points, i.e., 120 and 130 °C respectively, due to the reduction in intermolecular π-π interaction among the Pc rings caused by the steric hindrance of 2,6-dihexyloxybenzene units. The thermal behaviors were investigated with temperature-controlled polarizing optical microscopy, differential scanning calorimetry, powder X-ray diffraction, and absorption spectral analyses. Pc 1, having C_4h molecular symmetry, organized into a lamellar structure containing lateral assemblies of Pc rings. In contrast, the other Pc 2 revealed the formation of metastable crystalline phases, including disordered stacks of Pcs due to rapid cooling from a melted liquid.     

Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II)

A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2′:6′,2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI–TOF mass spectrometry, UV–Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311–577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications.     

Macrocyclic Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity

We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes.     

Thermodynamic Control of Domain Swapping by Modulating the Helical Propensity in the Hinge Region of Myoglobin

Domain swapping is an exception to Anfinsen's dogma, and more than one structure can be produced from the same amino acid sequence by domain swapping. We have previously shown that myoglobin (Mb) can form a domain‐swapped dimer in which the hinge region is converted to a helical structure. In this study, we showed that domain‐swapped dimerization of Mb was achieved by a single Ala mutation of Gly at position 80. Multiple Ala mutations at positions 81 and 82 in addition to position 80 facilitated dimerization of Mb by stabilization of the dimeric states. Domain swapping tendencies correlated well with the helical propensity of the mutated residue in a series of Mb mutants with amino acids introduced to the hinge region. These findings demonstrate that a single mutation in the hinge loop to modify helical propensity can control oligomer formation, providing new ideas to create high‐order protein oligomers using domain swapping.     

Triallylstannyllithium-allyllithium as an initiator for the anionic reversible chain transfer polymerization of 1,3-butadiene

The anionic polymerization of 1,3-butadiene using a novel metalloidal anion initiator, triallylstannyllithium (TALi)-allyllithium (ALi), was studied. The TALi-ALi initiated anionic polymerization of 1,3-butadiene gave the star polymer along with the linear polybutadiene (PBD). The star polymer consisted of three PBD branches and a central tin atom. What is striking is a fact that the number-average molecular weights (M_n) and molecular weight distribution of three PBD branches and linear PBD were almost identical. A reversible chain transfer polymerization mechanism, which includes the equilibrium between tri(macroallyl)-stannyllithium and macroallylic anion, is proposed. © 1996 John Wiley & Sons, Inc.     

三甲基硅烷基丙炔与五甲基二硅烷基丙炔共聚物膜及其气体透过性

研究了三甲基硅烷基丙块与五甲基二硅烷基丙块共聚物〔poly(TMSP-co-PMDSP)〕的成膜特点。poly(TMSP-co-PMDSP)膜的气体透过系数分别为:P_(O2):4×10~3～12×10~3,P_(N2):3×10~3～8×10~3和P_(CO2):2×10~4～4×10~4barrer,气体透过稳定性低,透过行为偏离第二Fick定律,过系数下降,其中溶解系数降低的比例远大于扩散系数的增加比例,在含有凝聚性气体的环境里,膜的气体透过出现表面吸附控制的特征。     

Proton Conduction at High Temperature in High-Symmetry Hydrogen-Bonded Molecular Crystals of RuIII Complexes with Six Imidazole-Imidazolate Ligands

A new H-bonded crystal [Ru^III(Him)₃(Im)₃] with three imidazole (Him) and three imidazolate (Im⁻) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the Ru^III complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10⁻⁵ S cm⁻¹ at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [Ru^III(Him)₃(Im)₃] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state ²H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered.