J. Appl. Cryst.の発刊に際して

3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20874-922.pdf

The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†

2.2.1. Polyisocyanates 6117 2.2.2. Polysilanes 6118 2.2.3. Polyacetylenes 6120 2.3. Foldamer-Based Helical Polymers 6124 2.3.1. Click Polymerization 6126 2.3.2. Ring-Closing Reaction 6126 2.4. Other Types of Helical Polymers 6127 2.4.1. π-Conjugated Helical Polymers 6127 2.4.2. Metallosupramolecular Helical Polymers 6128 2.5. Induced Helical Polymers 6130 2.5.1. Induced Helical Polyacetylenes 6130 2.5.2. Other Induced Helical Polymers and Oligomers 6132

Helical polymers: synthesis, structures, and functions

In this review, we describe the recent advances in supramolecular helical assemblies formed from chiral and achiral small molecules, oligomers (foldamers), and helical and nonhelical polymers from the viewpoints of their formations with unique chiral phenomena, such as amplification of chirality during the dynamic helically assembled processes, properties, and specific functionalities, some of which have not been observed in or achieved by biological systems. In addition, a brief historical overview of the helical assemblies of small molecules and remarkable progress in the synthesis of single-stranded and multistranded helical foldamers and polymers, their properties, structures, and functions, mainly since 2009, will also be described.

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions

This Focus Review describes the emerging class of near-infrared (NIR) organic compounds containing the conjugated polyene, polymethine, and donor-acceptor chromophores and exploration of their NIR-absorbing, NIR-fluorescence, and NIR-photosensitizing properties for potential applications in heat absorbers, solar cells, and NIR light-emitting diodes Examples of NIR organic compounds are reviewed with emphasis on the molecular design, NIR absorption, and fluorescence and particular emerging applications The donor-acceptor type of NIR chromophores are particularly introduced owing to some unique features, including the designer-made energy gaps, facile synthesis, good processability, and controllable morphology and properties in the solid state Future directions in research and development of NIR organic materials and applications are then offered from a personal perspective

Near‐Infrared Organic Compounds and Emerging Applications

Co-oligomers involving (1H)-4-pyridone and 4-alkoxypyridine rings were studied, and it was found that their supramolecular transformation was caused by saccharide recognition. In the co-oligomers, pyridone and pyridine rings are alternately linked at their 2,6-position with an acetylene bond. The pyridine rings behave as a hydrogen bonding acceptor, and the pyridone rings and tautomerized 4-pyridinol work as a donor. Pyridine−pyridone−pyridine 3-mer was found to self-dimerize on the basis of vapor pressure osmometry in CHCl3, and the association constant was obtained as 2.3 × 103 M−1 by 1H NMR titration. Longer 5-, 7-, 9-, and 11-mer oligomers showed considerable broadening and anisotropy in the 1H NMR spectra due to self-association. These longer oligomers recognized octyl β-d-glucopyranoside and changed their form into a chiral helical complex, showing characteristic circular dichroism.

Saccharide recognition-induced transformation of pyridine-pyridone alternate oligomers from self-dimer to helical complex.

Magnesium phthalocyanine (MgPc) is a blue pigment whose X-phase is known to exhibit an intense near-IR-absorption. Because of this, MgPc has attracted attention as a material useful for laser print...

Interpretation of the Near-Infrared Absorption of Magnesium Phthalocyanine Complexes in Terms of Exciton Coupling Effects

Novel unsymmetrical squarylium dyes which absorb in the near-infrared region were synthesized by a stepwise procedure via intermediate 4-substituted 3-hydroxycyclobut-3-ene-1,2-diones. By introducing benz[c,d]indoline or benzo[b]pyran moieties at one end as an electron-donating component, the SQ dyes exhibited their absorption maxima at 739–821 nm with large molar absorption coefficients (log e = 4.96–5.18) in CHCl3. The X-ray analysis for one of these dyes was also examined to confirm the overall structure of the unsymmetrical SQ dye.

Synthesis of novel unsymmetrical squarylium dyes absorbing in the near-infrared region

As pointed out in titanylphthalocyanine, molecular distortion (reduction in molecular symmetry) upon crystallization exerts a significant influence on the optical absorption in the near-IR region. The electronic spectra of β metal-free phthalocyanine (MfPc) has been investigated from the standpoint of molecular distortion and exciton coupling effects. Close examination of the crystal structure of MfPc revealed that the molecular symmetry is reduced from D2h to Ci on going from solution to the solid state. Molecular distortion is found to enhance the band splitting in such a way that the longer-wavelength band is more displaced toward longer wavelengths while the shorter-wavelength band is more shifted toward shorter wavelengths. The electronic spectra of MfPc can mostly be interpreted in terms of the distortion of molecular framework. However, some exciton coupling effect is also observed, as shown by polarized reflection spectra on single crystals as well as the temperature dependence of absorption spectra.

Shinya Matsumoto

Papers

Saccharide recognition-induced transformation of pyridine-pyridone alternate oligomers from self-dimer to helical complex.

Interpretation of the Near-Infrared Absorption of Magnesium Phthalocyanine Complexes in Terms of Exciton Coupling Effects

Synthesis of novel unsymmetrical squarylium dyes absorbing in the near-infrared region

Molecular Distortion and Exciton Coupling Effects in β Metal-Free Phthalocyanine

Ambipolar organic field-effect transistors based on solution-processed single crystal microwires of a quinoidal oligothiophene derivative