‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

DNA electrochemistry through the base pairs not the sugar-phosphate backbone

Using intercalated, covalently bound daunomycin as a redox probe, ground state charge transport in DNA films with a perturbation in base pair stacking was examined in comparison with breaks in the sugar-phosphate backbone. While the introduction of one or even two nicks in the sugar-phosphate backbone yields no detectable effect on electron transfer, a CA mismatch significantly attenuates the electron transfer yield. These results confirm that the base pair stack is the pathway for DNA-mediated charge transfer, not the sugar-phosphate backbone.     

Cover Picture: Electrochemical Oxidative Csp3—H/S—H Cross‐Coupling with Hydrogen Evolution for Synthesis of Tetrasubstituted Olefins (Chin. J. Chem. 6/2019)

The inside cover picture shows an electrochemical oxidative Csp³‐H/S‐H activation with hydrogen evolution for the synthesis of tetrasubstituted olefins. This method features very high atom economy, besides hydrogen gas, under the base‐free, transition met‐al‐free, and oxidants‐free conditions, no other by‐products were generated. More details are discussed in the article by Lei et al. on page 547–551.

     

Selective binding of the cyano group in acrylonitrile adsorption on Si(100)-2 x 1

The covalent binding of acrylonitrile (CH(2)=CH-C triple bond N) and the formation of a C=C-C=N structure on Si(100) have been investigated using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) calculations. For chemisorbed acrylonitrile, the absence of nu(C triple bond N) at 2245 cm(-1) and the appearance of nu(C=N) at 1669 cm(-1) demonstrate that the cyano group directly participates in the interaction with Si(100), which is further supported by XPS and UPS observations. Our experimental results and DFT calculations unambiguously demonstrate a [2 + 2] cycloaddition mechanism for acrylonitrile chemisorption on Si(100) through the binding of C triple bond N to Si dimers. The resulting chemisorbed monolayer with a C=C-C=N skeleton can serve as a precursor for further chemical syntheses of multilayer organic thin films in a vacuum and surface functionalization for in situ device fabrication.     

Preparation of Mn3O4 nanocrystallites by low-temperature solvothermal treatment of γ-MnOOH nanowires

The preparation of trimanganese tetroxide (Mn₃O₄) nanocrystallites from γ-MnOOH nanowires under mild conditions has been achieved by two steps: first, γ-MnOOH nanowires with a mean diameter of about 12 nm and lengths of up to several micrometers were directly prepared via hydrothermal reaction between KMnO₄ and toluene in water at 180°C for 24 h; then, pure Mn₃O₄ nanocrystallites could be obtained by solvothermal treatment of the γ-MnOOH nanowires in ethylenediamine (EDA) and ethylene glycol (EG) at 150°C for 24 h. It was found that the Mn₃O₄ product obtained in EDA comprised well-defined nanocrystallites with the size in the range of 15-35 nm, while the one obtained in EG consisted of aggregated nanoparticles with the size of less than 18 nm.The possible formation mechanism of nanocrystalline Mn₃O₄ in EDA and EG and reasons for the different effects of various solvents on the products were also proposed.     

Heterophase ligand exchange and metal transfer between monolayer protected clusters

This paper describes reactions in which ligands are exchanged and metals are transferred between monolayer-protected metal clusters (MPCs) that are in different phases (heterophase exchange) or are in the same phase. For example, contact of toluene solutions of alkanethiolate-coated gold MPCs with aqueous solutions of tiopronin-coated gold MPCs yields toluene-phase MPCs that have some tiopronin ligands and aqueous-phase MPCs that have some alkanethiolate ligands. In a second example, heterophase transfer reactions occur between toluene solutions of alkanethiolate-coated gold MPCs and aqueous solutions of tiopronin-coated silver MPCs, in which tiopronin ligands are transferred to the former and gold metal to the latter phase. These ligand and metal exchange reactions are inhibited when conducted under N(2). The results implicate participation of an oxidized form of Au (such as a Au(I) thiolate, Au(I)-SR) as both a ligand and metal carrier in the exchange reactions. Au(I)-SR is demonstrated to be an exchange catalyst.     

Structural Tailoring of Monomolecular Films on Evaporated Silver Surface

Monomolecular films with well-defined structure were prepared by self-assembling of n-alkanoic acids on an evaporated silver surface. Here we report the structural studies of thin films of acids containing aromatic chromophores of varied size and polarity. Information regarding the packing, orientation and conformation of the structural units within the assembly were deduced from ellipsometric thickness measurement, polarized reflection absorption infrared spectra and wetting property measurement. Implications of results to the design of functional thin films are discussed.     

Use of deuterium–hydrogen exchange to characterize the fragmentation pathways of arteether and its metabolites in a thermospray mass spectrometer

Whereas the thermospray mass spectra of most compounds consist of only the pseudo-molecular ion with little fragmentation, the thermospray mass spectra of arteether (a cyclic endoperoxide) and its metabolites are relatively complex. Assignments of structures to individual fragments from normal spectra was particularly ambiguous because of uncertainties as to which fragments arose from ammonium ion or methanol adducts. In this study, these assignments could be resolved through the comparison of the regular spectrum with the deuterium-exchange spectrum (in an ND₄O₂CCH₃–CD₃OD–D₂O mobile phase) achieved using ‘sandwiched slug’ injection technique. The mass spectra of arteether and four of its metabolites all showed [M + ND₄]⁺ pseudo-molecular ions with greater than 91% H/D exchange, indicating a high efficiency with a minimal use of deuterated mobile phase. Most fragments showed H/D exchange rates in the 70–90% range and the isotope shift of individual spectral lines (ΔM) was found to be extremely useful in determining the structure of the fragment.     

超声波作用下羰基化合物的还原偶联反应

超声波在一些有机反应中有明显的促进作用「“，Luche等认为超声波的作用有两种主要类型［’j．一类是涉及电子转移的自由基或离子一自由基型反应，由于超声波的空化作用所产生的局部高温高压可以促进电子转移，从而明显地加快反应速度；对大多数离子型反应，超声波只能起到机械的物理作用．我们曾报道偕二卤化合物在Li、Na、Mg等金属作用下产生卡宾的反应是单电子转移过程，该反应可由于超声辐射而大大加速［‘］；而在芳基叔脚的断裂反应中，超声波可以促进三苯基俄与金属馊反应生成二苯基脚负离子，但对它进一步的亲核取代反应却没有明…