Facile synthesis of potassium tetrathiooxalate – The “true” monomer for the preparation of electron-conductive poly(nickel-ethylenetetrathiolate)

Polyethenetetrathiolate or polytetrathiooxalate? Improved synthesis, a comparative analysis of a prominent thermoelectric polymer and implications to the charge transport mechanism

“…Very recently, we proved that only one ring of TPD undergoes methanolysis under standard polymerization conditions and ett 4− is not formed even upon prolonged reaction of TPD and MeOK, presumably due to strong coulombic repulsions between the intermediate dithiolate anion, dmid 2− , and methoxy anions. 12 It was proposed that opening of the second ring requires the charge neutralization of dmid 2− either upon interaction with oppositely charged Ni 2+ (followed by the methanolysis of neutral Nidmid) or by oxidation of dmid 2− (i.e., via route C, Scheme 1). The importance of the oxidation process during the preparation of poly[K x (Ni-ett)] was stated in many previous papers and the polymerization process was performed in air, 13 iodine, 14 or by electrochemical reaction.…”

“…Particularly, we found that the intermediate dmid 2− formed upon the methanolysis of TPD undergoes a high-yield decarbonylation into tetrathiooxalate tto 2− , which may be formally considered as the oxidation product of the tetraanion ett 4− . 12 We postulated that tto 2− forms under the standard polymerization conditions and acts as the main comonomer which polymerizes with Ni 2+ salts, contributing to the formation of electrostatically neutral polymer fragments.…”

“…In this work, we benefit from the availability of the "true" monomer K 2 tto convenient synthesis which was developed in our previous work. 12 We assume that involvement in the polymerization of the "true" monomer instead of its precursor (TPD) should eliminate uncertainness associated with the complex polymerization mechanism, as discussed above. Second, the polymerization of the monomer tto 2− should lead to the "fully oxidized" polymer poly[Ni-tto] so that the problematic oxidation step can be avoided.…”

A Printable Paste Based on a Stable n-Type Poly[Ni-tto] Semiconducting Polymer

“…Polymer development. In this study, a poly[Ni-tto] polymer with good reproducible properties was synthesized according to the procedure described in detail in our previous articles [9,10]. Despite the formal difference between poly[Ni-tto] and the polynickelethenetetrathiolate (poly[K x (Ni-ett)]), which has been intensively studied over the past seven years [11][12][13][14][15][16], they both belong to the same class of coordination polymers and exhibit similar properties.…”

A one-dimensional π-d conjugated coordination polymer for sodium storage with catalytic activity in Negishi coupling

“…[16][17][18][29][30][31][32][33][34] These merits can be expected to benefit the long-term cycleability and the rate performance of batteries, which, however,has not been well investigated. On the other hand, although CCPs have been extensively studied, the exact chemical states or structures of most CCPs (for example,the valence of metal ions, [50] the single/double bond characters, [15,17] the presence or absence of counterions, [19,51] and radicals [15,17] )a re still unclear. Thes tructure and state variation during electrochemical redox process can be expected to provide an efficient method for revealing the chemical structures.I ti st herefore highly imperative to systematically investigate the chemical states of CCPs and their applications and inner mechanisms in batteries.…”