Molecular Alloys of Neutral Gold/Nickel Dithiolene Complexes in Single-Component Semiconductors

Mebrouk, Kenny; Kaddour, Wafa; Auban‐Senzier, Pascale; Pasquier, Claude; Jeannin, Olivier; Camerel, Franck; Fourmigué, Marc

doi:10.1021/acs.inorgchem.5b01059

Cited by 19 publications

(19 citation statements)

References 54 publications

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“…Metal dithiolene complexes have received a great deal of attention in recent years as potential molecular based functional materials, due to their high stability, magnetic, optical and conductive properties, which can be tuned through variation of the metal center or substitution pattern of the dithiolene ligands . In particular, neutral nickel and gold bis(1,2‐dithiolene) complexes have been studied as single component conductors, due to attractive features such as their square planar geometry and delocalized electronic structure, which leads to favorable intermolecular stacking interactions (a requirement for solid state conductivity) and reversible and tunable redox chemistry. Additionally, neutral gold dithiolene complexes can behave as Mott insulators, with one radical per site, resulting in an activation barrier for conductivity behavior that can be overcome with pressure .…”

Section: Introductionmentioning

confidence: 99%

High Ambipolar Mobility in a Neutral Radical Gold Dithiolene Complex

Mizuno

Benjamin

Shimizu

et al. 2019

Adv Funct Materials

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A new anionic gold dithiolene complex NBu 4 ·[1] is synthesized from the (1-((1,1-biphenyl)-4-yl-)-ethylene-1,2-dithiolene ligand 1, and the cis and trans isomers are separated by recrystallization. The trans isomer is oxidized via electrocrystallisation to the neutral gold dithiolene complex 2. Complex 2 crystalizes in 1D chains, held together by short (3.30-3.37 Å) S-S contacts, which are packed in a herringbone arrangement in the ab-plane. The complex exhibits semiconductor behavior (σ RT = 1.5 × 10 −4 S cm −1 ) at room temperature with a small activation energy (E a = 0.11 eV), with greater conductivity along the stacking direction. The charge transport behavior of complex 2 is further investigated in single-crystal field-effect transistor (FET) measurements, the first such measurements reported for gold dithiolene complexes. Complex 2 shows incredibly balanced ambipolar behavior in the single-crystal field-effect transistor (SC-FET), with high charge-carrier mobilities of 0.078 cm 2 V −1 s −1 , the highest ambipolar mobilities reported for metal dithiolene complexes. This well-balanced behavior, along with the activated conductivity and band structure calculations, suggests that 2 behaves as a Mott insulator. The magnetic properties are also studied by superconducting quantum interference device (SQUID) magnetometry and solid state 1 H NMR, with evidence of a nonmagnetic ground state at low temperature.

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Section: Introductionmentioning

confidence: 99%

High Ambipolar Mobility in a Neutral Radical Gold Dithiolene Complex

Mizuno

Benjamin

Shimizu

et al. 2019

Adv Funct Materials

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“…Nickel bis(dithiolene) complexes can be seen as inorganic analogues of the corresponding TTF-type donors where the metal replaces the central CC bond . Like TTF and its derivatives, they also have rich redox behavior and favorable solid-state interactions . Metal-bis(dithiolene) complexes are attracting increasing interest; for example, Mo-bis(dithiolene) complexes have been well studied as analogues of the active site in dimethyl sulfoxide reductase (DMSOR) .…”

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confidence: 99%

A Metal–Organic Framework Based on a Nickel Bis(dithiolene) Connector: Synthesis, Crystal Structure, and Application as an Electrochemical Glucose Sensor

Zhou

et al. 2020

J. Am. Chem. Soc.

110

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Functionalizing the redox-active tetrathiafulvalene (TTF) core with groups capable of coordination to metals provides new perspectives on the modulation of architectures and electronic properties of organic−inorganic hybrid materials. With a view to extending this concept, we have now synthesized nickel bis(dithiolene-dibenzoic acid), [Ni(C 2 S 2 (C 6 H 4 COOH) 2 ) 2 ], which can be considered as the inorganic analogue of the organic tetrathiafulvalene-tetrabenzoic acid (H 4 TTFTB). Likewise, [Ni(C 2 S 2 (C 6 H 4 COOH) 2 ) 2 ] is a redox-active linker for new functional metal−organic frameworks, as demonstrated here with the synthesis of(2) but is a better electrochemical glucose sensor due to the multiple oxidation−reduction states of the [NiS 4 ] core, which allow glucose to be oxidized to glucolactone by the high oxidation state [NiS 4 ] center. As a non-enzymatic glucose sensor, 1 on Cu foam (CF), 1-CF, was synthesized by a one-step hydrothermal method and exhibited an excellent electrochemical performance. The fabricated 1-CF electrode offers a high sensitivity of 27.9 A M −1 cm −2 , with a wide linear detection range from 2.0 × 10 −6 to 2.0 × 10 −3 M, a low detection limit of 1.0 × 10 −7 M (signal/noise = 3), and satisfactory stability and reproducibility.

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“…At 20 K and above, the T 1,s lifetimes for [Au 0.02 Ni 0.98 (adt) 2 ] match the frozen solution data, and run parallel up to the highest measurement temperature of 80 K. This profile is borne out of the planar structure of 2 and its diamagnetic host. Neutral gold bis(dithiolenes) are single component semiconductors,27,33,45,46 and the conductivity is tuned when doped into the corresponding neutral Ni complex 29. The planar molecules stack into dimerized columns with intermolecular distances as short as 3.6 Å, which is the source of the observed singlet-triplet magnetic behaviour in neutral gold bis(dithiolenes) 29,46…”

Section: Resultsmentioning

confidence: 99%