Infrared study of a thianthrenic polymer

Abstract

With the aim of finding insights into the as‐yet unclear chemical structure of thianthrenic polymers, a detailed IR analysis on a sample previously prepared by us is reported. The IR spectrum is interpreted mainly by way of two correlated reference units: the unsubstituted thianthrene and the 1,2,4,5‐tetrahalosubstituted benzene. Since a full interpretation of the spectrum of the thianthrene molecule is still lacking, we have tried a first assignment, taking o‐dihalobenzenes as component models. The spectrum of the polymer is found to correlate well with spectra of the reference moieties. Other units, taken into account to get the most reliable picture of the polymeric structure, seem to be present at appreciable concentrations. Our results lead us to propose the existence of regular, fully intramolecularly cyclized thianthrenic segments limited by defective units, mainly 1,2,4‐trithiosubstituted benzene. A narrow peak at 886 cm−1 can be interpreted as a regularity band, supporting the existence of chain segments where the repeat units are correlated by translational symmetry.

14n/15n Isotope Effect on the Electron Transfer Process Between Phenothiazine and Its Radical Cation

“…The Raman spectral assignment of phenothiazine is in accordance with those reported previously. 13,15 The assignment for [ 15 N]phenothiazine is straightforward since it showed similar IR and Raman spectra to those of its 14 N analogue and some low-frequency shifts are obvious due to the heavy isotope substitution.…”

“…1 H NMR spectra were recorded on a Bruker AM 400 NMR spectrometer operating at 400 MHz. The molar ratio of phenothiazine to [ 15 N]phenothiazine was obtained by integrating the singlet and doublet peak areas of 14 N-H and 15 N-H, respectively, and each spectrum was integrated three times to ensure that the deviation was within 10%. The NMR result was checked with a standard sample, which gave the expected PT/[…”

“…In view of these arguments, we were motivated to see if a similar EIE exists in electron transfer processes between radical cations and their neutral molecule precursors, which had never been studied before our previous reports on the significant 1 H/ 2 H and 32 S/ 33 S EIEs on the electron exchange of thianthrene and its radical cation. [9][10][11] Here we report electron paramagnetic resonance (EPR), IR and Raman spectroscopic studies and physical separation results on the 14 ; (d) computer simulation of (c) generated by using a molar ratio of PT +• to [15N]PT +• of 1 : 1·28, corresponding to K = 0·78 for reaction (2) rium of thianthrene and its radical cation, in which an electron is transferred preferentially from the perdeuterated molecule to the perprotio radical cation [K = 0·62 for equation (3)]. 9 The result is also in general agreement with the EIEs in the electron transfer processes of radical anions and their molecule precursors reported by Stevenson and co-workers.…”

Novel Approach to Ladder-Type Polymers: Polydithiathianthrene via the Intramolecular Acid-Induced Cyclization of Methylsulfinyl-Substituted Poly(meta-phenylene sulfide)

“…The most promising candidate in this context was the 1,3-di(2-methylsulfinylphenylene)benzene (17). 17 was synthesized in 55% yield by reacting dithioresorcin (18) with 2-fluoro-methylsulfinylbenzene (19) in the presence of potassium carbonate (Scheme 7).…”

Synthesis and Characterization of Semiconductive Dichloridobis(thianthrene)gold(1+) Tetrachloridoaurate(1–)

“…The IR vibrational spectrum of thianthrene has been thoroughly studied. [13,14] The obvious differences in the spectra appear predominantly for C-S vibrations but are also present for C-C and C-H modes. For example, the stretching out-of-plane deformation modes, observed for thianthrene at 476, 1086 and 1101 cm - .…”