Synthesis of new tetrathiafulvalenes with aromatic substituents and related metallic dithiolene complexes

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

“…This chemical approach has been successfully developed for the synthesis of mono and bis-pyridyl-TTFs (Scheme 4) [13][14][15] and was also extended to the synthesis of 3-quinolyl and 3,5-pyrimidyl [13] derivatives 10 and 11. The mono and bis-pyridyl-TTFs can also be prepared from the unsymmetrical or symmetrical coupling using the 4-pyridyl-1,3-dithiole-2-one in the presence of neat triethylphosphite but in rather low yields [16][17][18]. The pyridine substituent directly linked to the donor core has no significant electron withdrawing effect on the redox properties of the donor core as the oxidation potentials remain very close to those of the non-substituted TTFs [10][11][12][13][14][15][16][17] (Table 1).…”

“…The metallacycle is folded by 28.2 • about the P· · ·P axis, while the TTF units are only slightly bended by 16.1 • about the S· · ·S hinge of the inner dithiole halves. The values for the central C C and C S bonds are indicative for the neutral state of the donor.…”

“…Investigation of the magnetic properties of Cu6 and Cu7 showed a Curie-type behavior attributed to the presence of non-interacting Cu(II) species with g = 2.12-2. 16.…”

Synthesis and properties of alkynethiolate gold(i) complexes

“…37, 38 To the best of our knowledge the reported metallopolymer is the first example with alkynethiolate units. 40 Subsequently, we extended this work to new thiadiazoles using 2-thiophene and 3-thiophene as ligands (3 and 4) considering the interesting properties that thiophene ligands can contribute to alkynethiolate and dithiolene complexes. Thiadiazole 5 was chosen in order to improve the solubility of the final alkynethiolate complexes that would then allow the growth of suitable crystals for X-ray diffraction.…”

Crystal structure of (RBzPy)n[Ni(4-pedt)2] salts engineering by pyridine ring arrangements

“…The 4-(4-pyridyl)-1,3-dithiol-2-one was synthesised according to literature reports. 13,14 Elemental analyses of the compounds isolated in these studies were performed at ITN analytical services using an EA 110 CE Instruments automatic analyzer. p-BrBzPy[Ni(4-pedt) 2 ]: on a round-bottom Schlenk flask, the 4-(4-pyridyl)-1,3-dithiol-2-one (0.200 g, 1.02 mmol) was added to a freshly prepared sodium methoxide solution (0.048 g, 2.04 mmol, 10 cm 3 ) and stirred for 1 h. A solution of NiCl 2 .6H 2 O (0.12 g, 0.52 mmol) in methanol (10 cm 3 ) was added to the dark red mixture and allowed to stir for another hour.…”