Origin of the High Electrical Conductivity of Neutral [Ni(ptdt)<sub>2</sub>] (ptdt<sup>2-</sup> = propylenedithiotetrathiafulvalenedithiolate):  A Route to Neutral Molecular Metal

Kobayashi, Akiko; Tanaka, Hisashi; Kumasaki, Mieko; Torii, Hajime; Narymbetov, B.Zh.; Adachi, Toshiaki

doi:10.1021/ja9921017

Cited by 80 publications

(92 citation statements)

References 19 publications

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“…1 Although [Ni(ptdt) 2 ] did not exhibit metallic properties, it exhibited high conductivity. This high conductivity of the crystal convinced us of the validity of our idea regarding the design of a single-component molecular metal.…”

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Single-component Layered Molecular Conductor, [Au(ptdt)2]

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A single-component layered molecular conductor, [Au(ptdt) 2 ] (ptdt: propylenedithiotetrathiafulvalenedithiolate) was prepared. Unlike the single-component molecular metal, [Au(tmdt) 2 ] (tmdt: trimethylenetetrathiafulvalenedithiolate) exhibiting three-dimensional compact molecular packing and antiferromagnetic transition at 110 K, the compressed pellet of the microcrystals of [Au(ptdt) 2 ] exhibited fairly high conductivity and small temperature-independent paramagnetic susceptibility.In 1999, the crystal structure and electrical properties of a single-component molecular conductor, [Ni(ptdt) 2 ] (Chart 1), were reported.1 Although [Ni(ptdt) 2 ] did not exhibit metallic properties, it exhibited high conductivity. This high conductivity of the crystal convinced us of the validity of our idea regarding the design of a single-component molecular metal.2 Two years later, the first single-component molecular metal, [Ni(tmdt) 2 ], was realized by using an analogous extended-TTF-type (TTF: tetrathiafulvalene) dithiolate ligand, tmdt.3 The observation of de Haasvan Alphen oscillations at very high magnetic fields and low temperatures as well as ab initio band structure calculations proved the existence of the three-dimensional (3D) Fermi surfaces (FSs). 4,5 To date, various single-component molecular metals including a series of isostructural [M(tmdt) 2 ] (M = Ni, Cu, Pd, Au, and Pt) systems have been reported. 6 The high controllability of the electronic band structure achieved by exchanging the central metal atom (M) for another transition metal is an important characteristic of the single-component molecular conductor. The electronic band structure of [M(tmdt) 2 ] near the Fermi level is determined mainly by three molecular orbitals, namely, sym-L³, asym-L³(d), and pd·(¹) orbitals (Figure 1). 8 The sym-L³ and asym-L³(d) orbitals form 3D stable metal bands in the Ni, Pd, and Pt complexes with an even number of total electrons. On the other hand, the asym-L³(d) orbital becomes the singly occupied molecular orbital (SOMO) of Au(tmdt) 2 with an odd number of total electrons, and [Au(tmdt) 2 ] becomes a magnetic metal exhibiting antiferromagnetic transition at 110 K (in this paper, [M(tmdt) 2 ] and M(tmdt) 2 represent the crystal of a singlecomponent molecular conductor and the constituent molecule, respectively). 9 In the case of [Cu(tmdt) 2 ], pd·(¹) becomes the SOMO and an antiferromagnetic chain coexists with ³ conduction electrons. 10In addition to the frontier molecular orbital properties, the mode of molecular arrangement, which is controllable to a certain extent by the type of ligand (L) used, plays a crucial role in the determination of the band structure of a single-component molecular conductor [M(L) 2 ]. A variety of electronic structures can be realized by using different combinations of M and L. However, the role of L, especially the bulkiness of the terminal alkyl group of L has not been investigated sufficiently. In this work, [Au(ptdt) 2 ] was prepared in order to study the effect of the terminal alk...

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Single-component Layered Molecular Conductor, [Au(ptdt)2]

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“…In 1999, Kobayashi et al also reported the highly conductive semiconductor 34 (' RT ¼ 7 S cm À1 , " g ¼ 0:06 eV for single crystal). 130 They analyzed its purity by EPMA, which gives about one order less accuracy than the elemental analysis. Although numerous reports on highly conductive single component coordination compounds have appeared since 2000, [131][132][133][134][135][136][137][138][139][140] the characterizations of some compounds are insufficient to claim the metallic single molecular solid, concerning the purity, measurement conditions, experimental information, etc.…”

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Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

Saito¹,

Yoshida²

2007

Bulletin of the Chemical Society of Japan

371

127

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“…Ab initio calculations of the singlet and lowest lying triplet energies of isolated molecules of [Ni(ptdt) 2 ] indicate that this molecule possesses a very small HOMO-LUMO gap. 15 Tight-binding Hückel calculations suggest that the crystal possesses a quasi-one-dimensional electronic band structure of a crossing-band type. 15 At ambient pressure, a Fermi surface exhibiting small electron and hole pockets is stabilised by transverse intermolecular interactions.…”

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“…15 Tight-binding Hückel calculations suggest that the crystal possesses a quasi-one-dimensional electronic band structure of a crossing-band type. 15 At ambient pressure, a Fermi surface exhibiting small electron and hole pockets is stabilised by transverse intermolecular interactions. This, in conjunction with the temperature-dependent resistivity of the crystal, has been taken as evidence that it is a narrow-band semiconductor, [13][14][15][16] whilst the stability of this semiconducting structure up to approximately 19 GPa indicates that the crystal possesses a crossing-band electronic structure up to high pressures.…”

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“…15 At ambient pressure, a Fermi surface exhibiting small electron and hole pockets is stabilised by transverse intermolecular interactions. This, in conjunction with the temperature-dependent resistivity of the crystal, has been taken as evidence that it is a narrow-band semiconductor, [13][14][15][16] whilst the stability of this semiconducting structure up to approximately 19 GPa indicates that the crystal possesses a crossing-band electronic structure up to high pressures. 13 To understand the remarkable stability of the semiconducting state in this crystal, and possible structural changes that may result in the stabilisation of a metallic state at high pressure, demands a detailed knowledge of the crystal's electronic structure.…”

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The high-pressure electronic structure of the [Ni(ptdt)2] organic molecular conductor

Tulip

Bates

Clark

2012

The Journal of Chemical Physics

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Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. The electronic structure of the single component molecular crystal [Ni(ptdt) 2 ] (ptdt = propylenedithiotetrathiafulvalenedithiolate) is determined at ambient and high pressure using density functional theory. The electronic structure of this crystal is found to be of the "crossing bands" type with respect to the dispersion of the HOMO and LUMO, resulting in a small, non-zero density of states at the Fermi energy at ambient pressure, indicating that this crystal is a "poor quality" metal, and is consistent with the crystal's resistivity exhibiting a semiconductor-like temperature dependence. The ambient pressure band structure is found to be predominantly one-dimensional, reflecting enhanced intermolecular interactions along the [100] stacking direction. Our calculations indicate that the band structure becomes two-dimensional at high pressures and reveals the role of shortened intermolecular contacts in this phenomenon. The integrity of the molecular structure is found to be maintained up to at least 22 GPa. The electronic structure is found to exhibit a crossing bands nature up to 22 GPa, where enhanced intermolecular interactions increase the Brillouin zone centre HOMO-LUMO gap from 0.05 eV at ambient pressure to 0.15 eV at 22 GPa; this enhanced HOMO-LUMO interaction ensures that enhancement of a metallic state in this crystal cannot be simply achieved through the application of pressure, but rather requires some rearrangement of the molecular packing. Enhanced HOMO-LUMO interactions result in a small density of states at the Fermi energy for the high pressure window 19.8-22 GPa, and our calculations show that there is no change in the nature of the electronic structure at the Fermi energy for these pressures. We correspondingly find no evidence of an electronic semiconducting-metal insulator transition for these pressures, contrary to recent experimental evidence [Cui et al., J. Am. Chem. Soc. 131, 6358 (2009)].

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Origin of the High Electrical Conductivity of Neutral [Ni(ptdt)₂] (ptdt^2- = propylenedithiotetrathiafulvalenedithiolate): A Route to Neutral Molecular Metal

Cited by 80 publications

References 19 publications

Single-component Layered Molecular Conductor, [Au(ptdt)2]

Single-component Layered Molecular Conductor, [Au(ptdt)2]

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

The high-pressure electronic structure of the [Ni(ptdt)2] organic molecular conductor

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Origin of the High Electrical Conductivity of Neutral [Ni(ptdt)2] (ptdt2- = propylenedithiotetrathiafulvalenedithiolate): A Route to Neutral Molecular Metal

Cited by 80 publications

References 19 publications

Single-component Layered Molecular Conductor, [Au(ptdt)2]

Single-component Layered Molecular Conductor, [Au(ptdt)2]

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

The high-pressure electronic structure of the [Ni(ptdt)2] organic molecular conductor

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Origin of the High Electrical Conductivity of Neutral [Ni(ptdt)₂] (ptdt^2- = propylenedithiotetrathiafulvalenedithiolate): A Route to Neutral Molecular Metal