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Molecules 2018, 23(2), 424; https://doi.org/10.3390/molecules23020424

Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes

C2TN, Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, E.N. 10 ao km 139.7, 2695-066 Bobadela LRS, Portugal
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Received: 19 January 2018 / Revised: 5 February 2018 / Accepted: 9 February 2018 / Published: 14 February 2018
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Abstract

Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3) and nickel dianionic species (n-Bu4N)x[Ni(α-mtdt)2] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu4N)2[Au2(α-tbtdt)2] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)2] (6) and [Ni(α-mtdt)2] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)2] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)2] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)2] are indicative that these compounds are single component molecular conductors. View Full-Text
Keywords: gold bisdithiolene complexes; nickel bisdithiolene complexes; thiophenetetrathiafulavalenedithiolate ligands; single component molecular conductors gold bisdithiolene complexes; nickel bisdithiolene complexes; thiophenetetrathiafulavalenedithiolate ligands; single component molecular conductors
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Silva, R.A.L.; Vieira, B.J.C.; Andrade, M.M.; Santos, I.C.; Rabaça, S.; Lopes, E.B.; Coutinho, J.T.; Pereira, L.C.J.; Almeida, M.; Belo, D. Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes. Molecules 2018, 23, 424.

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