Article

Cobaltacarboranylacetylene 8,8'-(μ-CHC-CH2S)-(1,2-C2B9H10)2-3Co(III): Synthesis, Characterization and Polymerization of New Substituted Acetylene

Collection of Czechoslovak Chemical Communications (Impact Factor: 1.14). 01/1996; 61(6):877-887. DOI: 10.1135/cccc19960877

ABSTRACT Synthesis, structure and properties of 8,8'-(μ-propargylthio)bis(1,2-dicarbollido)cobaltate, 8,8'-(μ-CHC-CH2S)-(1,2-C2B9H10)2-3-Co(III), are described (NMR, IR, and UV spectra, mass spectrum, X-ray structure, dipole moment) and transformation of this acetylenic monomer into a π-conjugated homopolymer is reported.

1 Bookmark
 · 
25 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: New functional acetylene, 1-ethynyl-4-iodobenzene, (p-iodophenylacetylene) was prepared, characterized (i.r., n.m.r., u.v. and mass spectra) and transformed into high-molecular-weight polymers. Various WOCl4-based and MoCl5-based catalysts were used in the polymerization, the former leading to the red soluble and the latter to dark red insoluble poly(p-iodophenylacetylene) (PIPA), respectively. Both types of PIPA are non-crystalline and they differ in the configurational structure which, however, could not be assigned with certainty. A too high molecular weight and/or cross-linking is suggested as a reason of insolubility of PIPA prepared on Mo-based catalysts. The soluble PIPA was found to degrade autoxidatively in tetrahydrofuran solution at room temperature obeying the kinetic laws of polymer random degradation. The determined value of the rate constant of degradation, 2.6 × 10−6 min−1, is slightly higher than that found for unsubstituted poly(phenylacetylene) (PPA), under the same conditions. PIPA was found to possess a higher photo-conductivity than PPA at low and moderate electric fields. The Onsager model offers an adequate explanation for the measured dependence of the photogeneration efficiency of the applied electric field assuming the Gaussian distribution of the radii of charge-transfer states.
    Polymer 01/1997; 38(13):3359–3367. · 3.77 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Metallacarboranes containing carborane ligands possessing a pentagonal open face can coordinate metal atoms in a η5-manner quite similar to the cyclopentadienyl monoanion, thus affording metallocene analogues. By virtue of such an analogy, their electron transfer aptitude plays an important role in their physico-chemical characterisation. We review such an aspect, also providing evidence for the structural consequences of their electron transfer processes.At variance with metallocenes, electrochemical investigations on the metallacarboranes have not yet become a routine tool to search for their potential application in fields which require electronic mobility.
    Coordination Chemistry Reviews 06/2006; 250:1351-1372. · 12.10 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: New stable polyacetylenes whose quantum yield of fluorescence is increased up to 62% because of the presence of pendant 4-(piperidine-1-yl)-1,8- naphtalimide groups are described. The polymers are prepared by two-step modification of copolymers of 1-(4-tert-butylphenyl)-6-chlorohex-1-yne and 1-phenylhex-1-yne consisting of the exchange of chlorine atoms at side groups for azide groups and subsequent Huisgen click reaction of the azide groups with ethynyl groups of N-(prop-1-yne-3-yl)-4-(piperidine-1-yl)-1,8-naphthalimide. Modification is evidenced by 1H NMR, IR, Raman and UV-vis spectroscopy. Modified polymers show the excitation energy transfer from their main chains on fluorophores and nearly preservation of fluorescence properties of fluorophores upon their binding to polymer chains.
    Macromolecular Chemistry and Physics 02/2012; 213(4):411-424. · 2.45 Impact Factor