Pd‐initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid‐containing products

Pd‐initiated polymerization and oligomerization of diazo compounds containing a dialkoxyphosphinyl group are described. Polymerization of 2‐dialkoxyphosphinylethyl diazoacetates with π‐allylPdCl‐based initiating systems afforded C? C main chain polymers bearing phosphonate on each main chain carbon atom. The quantitative transformation of the side chain phosphonate to phosphonic acid resulted in the formation of water soluble polymers having the acid groups accumulated around their main chains, although the carbonyl ester linkage in the side chain was cleaved via intramolecular acid‐assisted hydrolysis in water at 80 °C. Pd‐initiated oligomerization of diethyl diazomethylphosphonate yielded an oligomeric product bearing diethoxyphosphiny groups directly attached to its main chain carbons, with unexpected incorporation of azo group in the main chain framework. Hydrolysis of the phosphonate of the oligomer afforded a water‐soluble product, which was revealed to show higher proton conductivity than poly(vinylphosphonic acid) under certain conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1742–1751     

Synthesis,Structure, Optical,and Electrochemical Properties of Triple‐ and Quadruple‐Decker Co‐facial Tetrathiafulvalene Arrays

Understanding the details of the electronic structure in face‐to‐face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (‐S(CH₂)_nS‐, n=1–4) as models of triple‐ and quadruple‐decker TTF arrays. Single‐crystal X‐ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi‐electron transfers, depending on the length of the ‐S(CH₂)_nS‐ units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630–1850 nm), attributed to a mixed valence (MV) state of the triple‐ and quadruple‐decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent‐dependent redox processes were observed. Moreover, π‐trimers and π‐tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit.     

Catalytic Asymmetric Syntheses of Alkylidenecyclopropanes from Allenoates with Donor-Acceptor and Diacceptor Diazo Reagents

The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh₂((S)-TCPTAD)₄ or Rh₂((R)-BTPCP)₄ catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r.     

Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness

Chiral macrocyclic dimers, trimers, and tetramers composed of paraphenylene and tethered binaphthyl were synthesized, and their molecular structures and chiroptical properties were investigated. X-ray analysis and theoretical calculations revealed that multiple twisted molecular structures – dimers, trimers, and tetramers – adopt figure-of-eight, Möbius triangle, and concave rectangle structures, respectively. These homologues have large ϵ values in their UV-vis absorption spectra because of the π-conjugation of the naphthalene-phenylene-naphthalene frameworks. Owing to the shape-persistent ring structure and tethering with −OCH₂CH₂O−, high fluorescence quantum yields and a relatively high dissymmetry factor g_CPL in circularly polarized luminescence (CPL) spectra were achieved. This results in CPL brightness (B_CPL) of over 100, which is greater than that of the conventional organic CPL dye.     

Biomimetic Design of a Robustly Stabilized Folded State Enabling Seed-Initiated Supramolecular Polymerization under Microfluidic Mixing**

We have investigated the folding and assembly behavior of a cystine-based dimeric diamide bearing pyrene units and solubilizing alkyl chains. In low-polarity solvents, it forms a 14-membered ring through double intramolecular hydrogen bonds between two diamide units. The spectroscopic studies revealed that the folded state is thermodynamically unstable and eventually transforms into more energetically stable helical supramolecular polymers that show an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Importantly, compared to an alanine-based monomeric diamide, the dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well as an increased thermodynamic stability in the aggregated state. Accordingly, the initiation of supramolecular polymerization can be regulated using a seeding method even under microfluidic mixing conditions. Furthermore, taking advantage of a self-sorting behavior observed in a mixture of l -cysteine- and d -cysteine-based dimeric diamides, a two-step supramolecular polymerization was achieved by stepwise addition of the corresponding seeds.     

A Dicyanomethyl Radical Conjugated with a Pyridylamino Group: Combining Radical-based Dynamic Covalent Chemistry and Coordination Chemistry

In this work, we aimed to develop a dicyanomethyl radical that undergoes both reversible C−C bond formation/dissociation and metal-ligand coordination reactions to combine dynamic covalent chemistry (DCC) based on organic radicals with coordination chemistry. We have previously reported a dicyanomethyl radical conjugated with a triphenylamine ( 1 ⋅) that exhibits a monomer/dimer equilibrium between the σ-bonded dimer ( 1₂ ). We designed and synthesized a novel dicyanomethyl radical with a pyridyl group as a coordination point ( 2 ⋅) by replacing the phenyl group of 1 ⋅ with a 3-pyridyl group. We showed that 2 ⋅ is also in an equilibrium with the σ-bonded dimer ( 2₂ ) in solution and has suitable thermodynamic parameters for application in DCC. 2₂ coordinates to PdCl₂ in a 2 : 2 ratio to selectively form a metallamacrocycle ( 2₂ )₂(PdCl₂)₂, and its structure was clarified by single crystal X-ray analysis. Variable-temperature NMR, ESR, and electronic absorption measurements revealed that ( 2₂ )₂(PdCl₂)₂ also undergoes the reversible C−C bond formation/dissociation reaction. Ligand-exchange experiment showed that 2₂ was liberated from ( 2₂ )₂(PdCl₂)₂ by the addition of another ligand with a higher affinity for Pd^II. This work demonstrated that DCC based on dicyanomethyl radicals works orthogonally to metal-ligand coordination reactions.     

meso‐Dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Unusual cis Tautomeric Form

meso‐Monobenzoporphycene (mMBPc) and meso‐dibenzoporphycene (mDBPc), in which one or two benzene moieties are fused at ethylene‐bridged positions (meso‐positions) of porphycene, were prepared in an effort to further delocalize the π‐electrons within the porphycene molecule. mMBPc and mDBPc were fully characterized by mass spectrometry, ¹H and ¹³C NMR spectroscopy, and X‐ray crystallography. The longest‐wavelength Q‐bands of mMBPc and mDBPc are red‐shifted by 92 nm and 418 nm, respectively, compared to that of the unsubstituted porphycene (Pc). Electrochemical measurements indicate that the HOMO is destabilized and the LUMO is stabilized by the fused benzene moieties at the meso positions. Furthermore, both XPS and theoretical studies support the presence of a cis tautomeric form in the ground state of mDBPc, despite the fact that essentially all known porphycene derivatives adopt the trans tautomeric form.     

Efficient Synthesis,Structure, and Complexation Studies of Electron‐Donating Thiacalix[n]dithienothiophene

A series of thiacalix[n]dithiothiophenes (n=4–10) was prepared by a facile method and X‐ray analysis was used to determine the molecular structures of square‐ (4‐mer) and pentagonal‐shaped macrocycles (5‐mer). In the cyclic voltammograms, reversible multielectron redox processes, which are due to electronic delocalization, were observed at low oxidation potentials. The cyclic 4‐mer acted as a “Janus‐head” cavitand for two C₆₀ molecules, whereas the 5‐ and 6‐mer formed stable 1:1 complexes with C₆₀ .