Synthesis and Structure of ζ-(BEDT-TTF)2(I3)(I5) and (BEDT-TTF)2(I3)(T1I4): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization

Mark A. Beno; Urs Geiser; Kim L. Kostka; Hau H. Wang; Kevin S. Webb; Millicent Anne Firestone; K. Douglas Carlson; Luis Nuñez; Jack M. Williams; Myung Hwan Whangbo

doi:10.1021/ic00259a021

Synthesis and Structure of ζ-(BEDT-TTF)₂(I₃)(I₅) and (BEDT-TTF)₂(I₃)(T1I₄): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization

Mark A. Beno
, Urs Geiser
, Kim L. Kostka
, Hau H. Wang
, Kevin S. Webb
, Millicent Anne Firestone
, K. Douglas Carlson
, Luis Nuñez
, Jack M. Williams
, Myung Hwan Whangbo

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

Abstract

Chemical oxidation of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET, C₁₀S₈H₈) in benzonitrile solution by slow diffusion of iodine vapor produces a mixture of black lustrous crystals. These include the well-known a- and 0-(ET)₂I₃ phases, δ-(ET)I₃, and ε-(ET)₂(I₃)(I₈)_0.5, as well as a new phase, ζ-(ET)₂(I₃)(I₅). Single-crystal X-ray diffraction studies show that this latter salt is monoclinic, P2₁/a, with a = 15.113 (4) A, b = 15.993 (6) A, c = 18.159 (9) A, β =100.99 (3)°, V_c = 4308 (2) A³, and Z = 4. The crystal structure consists of two-dimensional sheets containing both ET donor molecules and I₃^-anions, and these mixed ET-I₃^-sheets are separated by layers of V-shaped I₅^- anions. This ζ-phase is structurally very similar to ε-(ET)₂(I₃)(I₈)₀₅, Four-probe resistivity measurements of single crystals of ε-(ET)₂(I₃)(I₈)_0.5and ζ-(ET)₂(I₃)(I₅) both prepared by the present chemical oxidation method show that, although these materials are metallic to temperatures as low as 1.7 K, they do not undergo transitions to the superconducting state. These findings were confirmed by radio-frequency (rf) field penetration depth measurements of the same samples, which failed to detect superconductivity down to temperatures of 0.5 K, Band electronic structure calculations based on the crystal structure parameters of ε-(ET)₂(I₃)(I₈)_0.5and ζ-(ET)₂(I₃)(I₅) predict semiconducting properties for stoichiometric crystals. Therefore, it is proposed that the observed metallic properties result from the presence of anion vacancies producing slightly nonstoichiometric crystals. A new salt (ET)₂(I₃)(T1I₄) was prepared by electrochemical oxidation, and a crystal structure study reveals that it is monoclinic, P2₁/n, with a = 8.348 (3) A, b = 15.294 (8) A, c = 34.217 (16) Å, β = 93.61(3)°, V_c = 4360 (3) A³, and Z = 4. As in the case of ε-(ET)₂(I₃)(I₈)_0.5and δ-(ET)₂(I₃)(I₅), (ET)₂(I₃)(T1I₄) consists of mixed two-dimensional sheets containing both ET donor molecules and I₃^-anions, which are separated by layers of tetrahedral T1I₄^-ions. The salt is a semiconductor, in agreement with our band structure calculations.

Original language	English
Pages (from-to)	1912-1920
Number of pages	9
Journal	Inorganic Chemistry
Volume	26
Issue number	12
DOIs	https://doi.org/10.1021/ic00259a021
State	Published - Jan 1 1987
Externally published	Yes

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10.1021/ic00259a021

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Beno, M. A., Geiser, U., Kostka, K. L., Wang, H. H., Webb, K. S., Firestone, M. A., Carlson, K. D., Nuñez, L., Williams, J. M., & Whangbo, M. H. (1987). Synthesis and Structure of ζ-(BEDT-TTF)₂(I₃)(I₅) and (BEDT-TTF)₂(I₃)(T1I₄): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization. Inorganic Chemistry, 26(12), 1912-1920. https://doi.org/10.1021/ic00259a021

@article{68cdaa0d74c741e6b71014e8742c2e45,

title = "Synthesis and Structure of ζ-(BEDT-TTF)2(I3)(I5) and (BEDT-TTF)2(I3)(T1I4): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization",

abstract = "Chemical oxidation of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET, C10S8H8) in benzonitrile solution by slow diffusion of iodine vapor produces a mixture of black lustrous crystals. These include the well-known a- and 0-(ET)2I3 phases, δ-(ET)I3, and ε-(ET)2(I3)(I8)0.5, as well as a new phase, ζ-(ET)2(I3)(I5). Single-crystal X-ray diffraction studies show that this latter salt is monoclinic, P21/a, with a = 15.113 (4) A, b = 15.993 (6) A, c = 18.159 (9) A, β =100.99 (3)°, Vc = 4308 (2) A3, and Z = 4. The crystal structure consists of two-dimensional sheets containing both ET donor molecules and I3-anions, and these mixed ET-I3-sheets are separated by layers of V-shaped I5- anions. This ζ-phase is structurally very similar to ε-(ET)2(I3)(I8)05, Four-probe resistivity measurements of single crystals of ε-(ET)2(I3)(I8)0.5and ζ-(ET)2(I3)(I5) both prepared by the present chemical oxidation method show that, although these materials are metallic to temperatures as low as 1.7 K, they do not undergo transitions to the superconducting state. These findings were confirmed by radio-frequency (rf) field penetration depth measurements of the same samples, which failed to detect superconductivity down to temperatures of 0.5 K, Band electronic structure calculations based on the crystal structure parameters of ε-(ET)2(I3)(I8)0.5and ζ-(ET)2(I3)(I5) predict semiconducting properties for stoichiometric crystals. Therefore, it is proposed that the observed metallic properties result from the presence of anion vacancies producing slightly nonstoichiometric crystals. A new salt (ET)2(I3)(T1I4) was prepared by electrochemical oxidation, and a crystal structure study reveals that it is monoclinic, P21/n, with a = 8.348 (3) A, b = 15.294 (8) A, c = 34.217 (16) {\AA}, β = 93.61(3)°, Vc = 4360 (3) A3, and Z = 4. As in the case of ε-(ET)2(I3)(I8)0.5and δ-(ET)2(I3)(I5), (ET)2(I3)(T1I4) consists of mixed two-dimensional sheets containing both ET donor molecules and I3-anions, which are separated by layers of tetrahedral T1I4-ions. The salt is a semiconductor, in agreement with our band structure calculations.",

author = "Beno, \{Mark A.\} and Urs Geiser and Kostka, \{Kim L.\} and Wang, \{Hau H.\} and Webb, \{Kevin S.\} and Firestone, \{Millicent Anne\} and Carlson, \{K. Douglas\} and Luis Nu{\~n}ez and Williams, \{Jack M.\} and Whangbo, \{Myung Hwan\}",

year = "1987",

month = jan,

day = "1",

doi = "10.1021/ic00259a021",

language = "English",

volume = "26",

pages = "1912--1920",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "12",

}

Beno, MA, Geiser, U, Kostka, KL, Wang, HH, Webb, KS, Firestone, MA, Carlson, KD, Nuñez, L, Williams, JM & Whangbo, MH 1987, 'Synthesis and Structure of ζ-(BEDT-TTF)₂(I₃)(I₅) and (BEDT-TTF)₂(I₃)(T1I₄): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization', Inorganic Chemistry, vol. 26, no. 12, pp. 1912-1920. https://doi.org/10.1021/ic00259a021

Synthesis and Structure of ζ-(BEDT-TTF)₂(I₃)(I₅) and (BEDT-TTF)₂(I₃)(T1I₄): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization. / Beno, Mark A.; Geiser, Urs; Kostka, Kim L. et al.
In: Inorganic Chemistry, Vol. 26, No. 12, 01.01.1987, p. 1912-1920.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis and Structure of ζ-(BEDT-TTF)2(I3)(I5) and (BEDT-TTF)2(I3)(T1I4)

T2 - Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization

AU - Beno, Mark A.

AU - Geiser, Urs

AU - Kostka, Kim L.

AU - Wang, Hau H.

AU - Webb, Kevin S.

AU - Firestone, Millicent Anne

AU - Carlson, K. Douglas

AU - Nuñez, Luis

AU - Williams, Jack M.

AU - Whangbo, Myung Hwan

PY - 1987/1/1

Y1 - 1987/1/1

N2 - Chemical oxidation of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET, C10S8H8) in benzonitrile solution by slow diffusion of iodine vapor produces a mixture of black lustrous crystals. These include the well-known a- and 0-(ET)2I3 phases, δ-(ET)I3, and ε-(ET)2(I3)(I8)0.5, as well as a new phase, ζ-(ET)2(I3)(I5). Single-crystal X-ray diffraction studies show that this latter salt is monoclinic, P21/a, with a = 15.113 (4) A, b = 15.993 (6) A, c = 18.159 (9) A, β =100.99 (3)°, Vc = 4308 (2) A3, and Z = 4. The crystal structure consists of two-dimensional sheets containing both ET donor molecules and I3-anions, and these mixed ET-I3-sheets are separated by layers of V-shaped I5- anions. This ζ-phase is structurally very similar to ε-(ET)2(I3)(I8)05, Four-probe resistivity measurements of single crystals of ε-(ET)2(I3)(I8)0.5and ζ-(ET)2(I3)(I5) both prepared by the present chemical oxidation method show that, although these materials are metallic to temperatures as low as 1.7 K, they do not undergo transitions to the superconducting state. These findings were confirmed by radio-frequency (rf) field penetration depth measurements of the same samples, which failed to detect superconductivity down to temperatures of 0.5 K, Band electronic structure calculations based on the crystal structure parameters of ε-(ET)2(I3)(I8)0.5and ζ-(ET)2(I3)(I5) predict semiconducting properties for stoichiometric crystals. Therefore, it is proposed that the observed metallic properties result from the presence of anion vacancies producing slightly nonstoichiometric crystals. A new salt (ET)2(I3)(T1I4) was prepared by electrochemical oxidation, and a crystal structure study reveals that it is monoclinic, P21/n, with a = 8.348 (3) A, b = 15.294 (8) A, c = 34.217 (16) Å, β = 93.61(3)°, Vc = 4360 (3) A3, and Z = 4. As in the case of ε-(ET)2(I3)(I8)0.5and δ-(ET)2(I3)(I5), (ET)2(I3)(T1I4) consists of mixed two-dimensional sheets containing both ET donor molecules and I3-anions, which are separated by layers of tetrahedral T1I4-ions. The salt is a semiconductor, in agreement with our band structure calculations.

AB - Chemical oxidation of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET, C10S8H8) in benzonitrile solution by slow diffusion of iodine vapor produces a mixture of black lustrous crystals. These include the well-known a- and 0-(ET)2I3 phases, δ-(ET)I3, and ε-(ET)2(I3)(I8)0.5, as well as a new phase, ζ-(ET)2(I3)(I5). Single-crystal X-ray diffraction studies show that this latter salt is monoclinic, P21/a, with a = 15.113 (4) A, b = 15.993 (6) A, c = 18.159 (9) A, β =100.99 (3)°, Vc = 4308 (2) A3, and Z = 4. The crystal structure consists of two-dimensional sheets containing both ET donor molecules and I3-anions, and these mixed ET-I3-sheets are separated by layers of V-shaped I5- anions. This ζ-phase is structurally very similar to ε-(ET)2(I3)(I8)05, Four-probe resistivity measurements of single crystals of ε-(ET)2(I3)(I8)0.5and ζ-(ET)2(I3)(I5) both prepared by the present chemical oxidation method show that, although these materials are metallic to temperatures as low as 1.7 K, they do not undergo transitions to the superconducting state. These findings were confirmed by radio-frequency (rf) field penetration depth measurements of the same samples, which failed to detect superconductivity down to temperatures of 0.5 K, Band electronic structure calculations based on the crystal structure parameters of ε-(ET)2(I3)(I8)0.5and ζ-(ET)2(I3)(I5) predict semiconducting properties for stoichiometric crystals. Therefore, it is proposed that the observed metallic properties result from the presence of anion vacancies producing slightly nonstoichiometric crystals. A new salt (ET)2(I3)(T1I4) was prepared by electrochemical oxidation, and a crystal structure study reveals that it is monoclinic, P21/n, with a = 8.348 (3) A, b = 15.294 (8) A, c = 34.217 (16) Å, β = 93.61(3)°, Vc = 4360 (3) A3, and Z = 4. As in the case of ε-(ET)2(I3)(I8)0.5and δ-(ET)2(I3)(I5), (ET)2(I3)(T1I4) consists of mixed two-dimensional sheets containing both ET donor molecules and I3-anions, which are separated by layers of tetrahedral T1I4-ions. The salt is a semiconductor, in agreement with our band structure calculations.

UR - https://www.scopus.com/pages/publications/33845281674

U2 - 10.1021/ic00259a021

DO - 10.1021/ic00259a021

M3 - Article

SN - 0020-1669

VL - 26

SP - 1912

EP - 1920

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 12

ER -

Synthesis and Structure of ζ-(BEDT-TTF)2(I3)(I5) and (BEDT-TTF)2(I3)(T1I4): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization

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Synthesis and Structure of ζ-(BEDT-TTF)₂(I₃)(I₅) and (BEDT-TTF)₂(I₃)(T1I₄): Comparison of the Electrical Properties of Organic Conductors Derived from Chemical Oxidation vs. Electrocrystallization