Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)2−

Synthesis of a chiral molecular metal which shows metallic behaviour down to at least 4.2 K.

Serendipitous isolation of a triazinone-based air stable organic radical: synthesis, crystal structure, and computation

Here we report the synthesis, isolation, and characterization of a dication salt, namely 4,6-bis(4,4′-bipyridinium)-1,3,5-triazin-2-one {12+(PF6)22−·2H2O1(PF6)2·2H2O}, and its radical cation salt, namely 4,6-bis(4,4′-bipyridinium)-1,3,5-triazin-2-one (1+˙PF6−1˙PF6).

DFT investigation on the mechanisms of Csp3–H functionalization of glycine derivatives induced by radical cation salt

The mechanism of Csp3–H functionalization between ethyl 2-(p-tolylamino)acetate and phenylethylene initiated by tris(4-bromophenyl)aminium hexachloroantimonate was elaborated based on DFT calculations.

A 4-cyanobenzene-ethylenedithio-TTF electron donor and its (1 : 1) triiodide radical cation salt; isomer effects in C–N⋯H–C interactions

A new isomer of the dissymmetric TTF derivative, 4-cyanobenzene-ethylenedithio-tetrathiafulvalene (4-CNB-EDT-TTF) (1), was prepared and compared with the previously reported 5-CNB-EDT-TTF.

Crystal structure and physical properties of radical cation salt based on 4,5-ethylenedioxy-4′-iodotetrathiafulvalene (EDO-TTF-I) with iodine bonding ability

The radical cation salt of 4,5-ethylenedioxy-4′-iodotetrathiafulvalene possessing iodine bonding ability afforded the β′-type molecular arrangement in dimerized Mott insulating state.

SYNTHESIS OF THE OXIDIZED FORM OF DITHIENO-TTF BY ELECTROCRYSTALLIZATION

General principles of the electrocrystallization technique in application to organic molecules are shown, as some historical background. Based on this, we were able to rationalize main variables in the experiment which are needed in order to get crystals of the oxidized form, that are suitable for further applications such as for example single crystal x-ray diffraction analysis or conductivity measurements. The biggest impact comes from such factors as choice of solvent and supporting electrolyte, which influence directly the solubility of both the starting compound and its oxidized form. Purity of all components is also paramount. In order to avoid formation of by-products, experiment is usually performed in a sealed U-shaped electrochemical cell with a glass filter between the anodic and cathodic compartments and under inert atmosphere such as argon or nitrogen. Other parameters considered here, such as temperature of the solution and intensity of the current, help to fine-tune the result, but have less impact on whether the crystallization will occur at all. It is also critical to maintain both parameters at constant values in order to obtain high quality single crystals. Galvanostatic oxidation mode is more favourable comparing to the potentiostatic as it allows steady rate of oxidation by providing fixed intensity of the electrical current and subsequently more stable rate of crystal grows, although potentiostatic mode or alternating current can be used to grow bigger amounts when quality of the single crystal is less important. Further we used this approach to electrocrystalize previously obtained by our group dithieno-TTF, based on the exTTF scaffold. According to the literature cyclic voltammetry data, dithieno-TTF undergoes reversible single-wave two electron oxidation to form bis-cation similar to classic exTTF, but in our case only radical-cation salt was obtained in a form of shiny, dark-red, needle-like single crystals. This could be attributed to its extremely low solubility and corresponding formation of the kinetic product, which correlate well with relatively fast crystallization just within 3 days. Another possibility is a comproportionation reaction involving the starting neutral molecule and oxidized dication.