A nonporous crystalline solid consisting of an organoarsenic platinum(II) complex, i.e., a mononuclear diiodoplatinum(II) complex trans-PtI(2)(cis-DHDAtBu)(2) (1) with cis-1,4-dihydro-1,4-dimethyl-2,3,5,6-tetrakis(tert-butoxycarbonyl)-1,4-diarsinine (cis-DHDAtBu), shows on-off solid-state luminescence switching through reversible solvent vapor uptake and escape. The on-off switching of solid-state luminescence was achieved without changing the structure or electronic state of the organoarsenic platinum(II) complex. 相似文献
The reaction of {C,N-[Fe(η5-C5H5)(η5-C5H3(CH2NMe2)-2)]}Li, (FcN)Li, with zinc chloride affords the diorganozinc complex (FcN)2Zn (1). In solution, 1 appears as a mixture of rac and meso diastereomers, whereas in the solid state it crystallizes solely as a rac diastereomer. The ratio of rac/meso diastereomers in solution is solvent-, temperature- and concentration-dependent, consistent with an intermolecular exchange between diastereomers. An intramolecular dynamic phenomenon involving dissociation and recoordination of Zn---N bonds was also observed. The reaction of 1 with zinc chloride yields the monoorganozinc compound (FcN)ZnCl (2) as a slightly soluble yellow microcrystalline powder. 相似文献
Summary: The first π‐conjugated poly(thioketene dimer) was synthesized via the homopolymerization of a silylthioketene dimer by a chemical oxidation‐reduction process. The polymerization of trimethylsilylthioketene dimer in the presence of FeCl3 (in CHCl3 at 70 °C for 24 h) gave the corresponding doped poly(thioketene dimer). After treatment of the doped polymer with an aqueous solution of ammonia, the neutral poly(thioketene dimer) was obtained with an incidental desilylation. The polymer obtained was soluble in DMF and DMSO. From gel permeation chromatographic analysis (DMF, polystyrene standards), the number‐average molecular weight of the polymer was found to be 7 460. The polymer showed low oxidation potentials derived from the thioketene dimer unit. An effective extension of the π‐conjugation was observed in the polymer.
Synthesis of π‐conjugated poly(thioketene dimer). 相似文献
Cage silsesquioxane, denoted as polyhedral oligomeric silsesquioxane (POSS) has high crystallinity to readily cause aggregation when it is induced into polymer side chain. In this work, side-opened POSS was employed to construct a bifunctional monomer for cyclopolymerization. The collapsed symmetry of the POSS core effectively reduced the crystallinity to realize homogeneous films, while a traditional POSS homopolymer formed turbid and brittle films. The obtained film showed high transparency and thermal stability. 相似文献
2‐Arnino‐4,5‐dihydro‐3‐thiophenecarbonitriles 1a‐c reacted with α,β‐unsaturated ketones (e.g. methyl vinyl ketone 2 and benzalacetone 3 ) in the presence of titanium(IV) chloride to give the corresponding Michael adducts 4a‐c and 5a‐c. Thermal treatment of compounds 4a‐c and 5a‐c with titanium(IV) chloride caused intramolecular cyclocondensation to yield the corresponding tetrahydrothieno[2,3‐b]pyridines 6a‐c and 7a‐c. Aromatization of 6a‐c and 7a‐c with potassium tert‐butoxide in refluxing tert‐butyl alcohol pro ceeded smoothly to afford the corresponding dihydrothieno[2,3‐b]pyridines 8a‐c and 9a‐c. 相似文献
Organoarsenic chemistry was actively studied until the middle of 20th century. Although various properties of organoarsenic compounds have been computationally predicted, for example, frontier orbital levels, aromaticity, and inversion energies, serious concern to the danger of their synthetic processes has restricted experimental studies. Conventional synthetic routes require volatile and toxic arsenic precursors. Recently, nonvolatile intermediate transformation (NIT) methods have been developed to safely access functional organoarsenic compounds. Important intermediates in the NIT methods are cyclooligoarsines, which are prepared from nonvolatile inorganic precursors. In particular, the new approach has realized experimental studies on conjugated arsenic compounds: arsole derivatives. The elucidation of their intrinsic properties has triggered studies on functional organoarsenic chemistry. As a result, various kinds of arsenic-containing π-conjugated molecules and polymers have been reported for the last few years. In this minireview, progress of this recently invigorated field is overviewed. 相似文献