Some Air-stable Unsymmetrical Nickel 1,2-Dithiolenes with Extended Tetrathiafulvalenedithiolato Ligands

Abstract

(where dmit is 1,3-dithiol-2-thione-4,5-dithiolate, dmio is 1,3-dithiol-2-one-4,5-dithiolate, dt is tetrathiafulvalendithiolate, tmdt is trimethylenetetrathiafulvalenedithiolate, etdt is ethylenedithiotetrathiafulvalenedithiolate, and ptdt is propylenedithiotetrathiafulvalenedithiolate) were prepared and characterized analytically, electrochemically and spectroscopically. In the solid state, the compounds exhibit optical absorption edges between 0.70 and 0.82 eV. Their LUMO and HOMO levels occur at ca. 4.5 and 5.3 eV, respectively.

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

“…[9,12,16]. Also, using the compounds of Figure 7 and selenium analogues, as starting materials, the preparation of (neutral) M 1,2-DTs is possible (see [9,14,36,[48][49][50]52,63,64]). The old method, using 1,2-diketones (or benzoins) as starting materials, was applied for the preparation of a number of neutral complexes.…”

“…The complexes [Ni(dpedt)(dmit)], [Ni(dpedt)(dddt)] and [Ni(dpedt)(dt)] were prepared by this method ( [9,48,49] and work in progress). Generally speaking, from a number N = 100 ligands of Tables 1-3, one can expect N(N + 1)/2 binary combinations, namely 5050 symmetrical and unsymmetrical complexes for each metal, by applying several methods of preparation.…”

“…For example [Ni(dddt) 2 ] 2 X are isostructural and exhibit metallic behavior as (ET) 2 X. In recent years, a number of symmetrical M 1,2-DT complexes based on extended TTF-dithiolato ligands, such as [Ni(dt) 2 ] [22,23] and some unsymmetrical such as [Ni(dt)(dmit)] [48,49] (Figure 6) and selenium analogues have been prepared and studied. A number of extended TTF-dithiolate ligands are tabulated in Table 3.…”

“…A number of extended TTF-dithiolate ligands are tabulated in Table 3. Dithiolene ligands could be coordinated as 1,2-enedithiolate dianions (as in Tables 1-3), neutral dithioketones or mixed valence thioketones-radical thiolate monoanions-and have been regarded both as innocent and non-innocent ligands [6][7][8][9][10]49,68]. These single component (neutral) complexes exhibit semiconducting or metallic behaviour.…”

“…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 …”