Solid‐State Properties (Electronic, Magnetic, Optical) of Dithiolene Complex‐Based Compounds

Neutral Metal 1,2-Dithiolenes: Preparations, Properties and Possible Applications of Unsymmetrical in Comparison to the Symmetrical

“…The neutral complexes may exist as planar monomers or form dimers with either metal-metal bonds or metal-sulfur (selenium) bonds. Most of M 1,2-DTs were found to be crystallized in centrosymmetric space group and, up to now, only three complexes have been found to be crystallized in non centrosymmetric space group (see [7,10,15,17,20,63,64,69,94,97]). The data from selected M 1,2-DTs are described here, starting from crystals with weak intermolecular interactions.…”

“…Both interstacking and intrastacking S-S intermolecular distances are ca. 4.5 Å, i.e., much larger than the sum of van der Waal's radii (3.7 Å), while in (Bu 4 N)[M(dmit) 2 ] these distances are 3.59-3.72 Å (see [20] and references therein). This means that the complex has an almost 3D structure, with weak S-S interactions.…”

“…The donor (push) or acceptor (pull) ability of the additional groups, plays an important role in the behavior concerning optical, conducting and superconducting properties of these materials. For example, the complexes [M(mnt) 2 ] [5] and [M(dmit) 2 ] [6] (see also [8,11,12,20]), of which the molecular formulas are shown in Figure 2 L15a (X = Et, X' = Pent), L15b (X = X' = iPr) L16 **** L17 (R, R several groups) L18 * L4a (X = Me), L4b (X = Br), L4c (X = F), L4d (X = CF 3 ), L4e (X = NO 2 ), L4f (X = Cl), L4g (X = CN), L4h (X = H), L4i (X = OMe); ** L9a (X = H), L9b (X = Me), L9c (X = Et), L9d (X = F), L9e (X = CF 3 ), L9f (X = tBu), L9g (X = C 6 H 6 ), L9h (X = COOH), L9i (X = COOMe), L9ji (X = OMe), L9k (X = OC 4 H 9 ), L9l (X = OC 8 On the other hand, the complexes [Ni(dddt) 2 ] [5] and [Ni(edo) 2 ] [14], of which the molecular formulas are shown in Figure 3, are based on ligands with donor ability and give cationic salts, which are conducting materials [13][14][15]21]. 2 and Ni(edo) 2 .…”

“…They are compared to those obtained from the corresponding TTFs and similar single component materials. More information concerning the ligands of Table 1 can be found in [6][7][8][9][10][11][12][13][14][15][16]20,21,24,[26][27][28]30,31,34,36,[48][49][50]53,[61][62][63][64]72,77,79,88,89,92,94,[100][101][102][103][104]. More information concerning the ligands of Table 2 can be found in the corresponding references for L1 [34], L2 [34,98], L3 [33,95,102], L4 …”

[Fe(sal2-trien)][Ni(dmit)2]: towards switchable spin crossover molecular conductors

“…4 For instance, electronic conduction derived from dithiolene complexbased compounds has received much attention. 5 In particular, compounds of the type (NR 4 ) x [M(dmit) 2 ] (0 , x , 1) with nonintegral oxidation state based on 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit) (NR 4 + 5 tetraalkylammonium cation, M 5 Ni, Pd, Pt) present interesting electric properties. Considering the anionic character of the [Ni(dmit) 2 ] n2 species (Scheme 1, left) and its redox lability as well as the cationic nature and redox stability of most iron(III) SC complexes such as [Fe(sal 2 -trien)] + (Scheme 1, right), 6 we have decided to combine them as building blocks to investigate the possible synergy properties stemming from the coexistence of SC and electronic conduction in the same lattice.…”