Molecular Semiconductors from Bifunctional Dithia- and Diselenadiazolyl Radicals. Preparation and Solid-State Structural and Electronic Properties of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se)

A. Wallace Cordes, Robert C. Haddon, Richard T. Oakley, Lynn Schneemeyer, Joseph V. Waszczak, Kelly M. Young, Neil M. Zimmerman

Research output: Contribution to journalArticle

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Abstract

The reactions of 1,4-phenylenebis[N,N,N′-tris(trimethylsilyl)amidine] with sulfur and selenium dichlorides yield, respectively, the l,4-phenylenebis(dithiadiazolium) and bis(diselenadiazolium) dichlorides l,4-[(E2N2C)C6H4(CN2E2)]Cl2 (E = S, Se). Reduction of these materials with triphenylantimony affords the corresponding diradical species 1,4-[(E2N2C)C6H4(CN2E2)], which can be purified by high vacuum sublimation. The crystal structures of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are both monoclinic, space group P21/n. The crystal packing consists of sheets of interleaved columns of weakly associated diradical units (dimers); the mean intradimer separation is 3.34/3.37 Å (E = S/Se), and the mean interdimer separation is 3.68/3.71 Å (E = S/Se). The sulfur compound is an insulator, but the selenium material has a room temperature pressed pellet resistivity of about 100 fi cm. Magnetic susceptibility measurements show the solids to be predominantly diamagnetic with variable amounts of paramagnetic defects in the lattice. While the exact mechanism of conduction remains to be established, these systems represent the first structurally characterized conducting materials constructed from neutral molecular radicals. Extended Hiickel band structure calculations reveal band gaps of 0.84/0.69 eV (E = S, Se) for the crystalline solids. The calculated band dispersions show a high degree of three-dimensionality; to our knowledge these are the most isotropic organic molecular solids yet to be reported.

Original languageEnglish
Pages (from-to)582-588
Number of pages7
JournalJournal of the American Chemical Society
Volume113
Issue number2
DOIs
StatePublished - 1 Jan 1991

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Semiconductors
Selenium
Electronic properties
Structural properties
Amidines
Sublimation
Semiconductor materials
Sulfur Compounds
Vacuum
Sulfur
Sulfur compounds
Magnetic susceptibility
Dispersions
Dimers
Band structure
Temperature
Energy gap
Crystal structure
Crystalline materials
Defects

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Cordes, A. Wallace ; Haddon, Robert C. ; Oakley, Richard T. ; Schneemeyer, Lynn ; Waszczak, Joseph V. ; Young, Kelly M. ; Zimmerman, Neil M. / Molecular Semiconductors from Bifunctional Dithia- and Diselenadiazolyl Radicals. Preparation and Solid-State Structural and Electronic Properties of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se). In: Journal of the American Chemical Society. 1991 ; Vol. 113, No. 2. pp. 582-588.
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abstract = "The reactions of 1,4-phenylenebis[N,N,N′-tris(trimethylsilyl)amidine] with sulfur and selenium dichlorides yield, respectively, the l,4-phenylenebis(dithiadiazolium) and bis(diselenadiazolium) dichlorides l,4-[(E2N2C)C6H4(CN2E2)]Cl2 (E = S, Se). Reduction of these materials with triphenylantimony affords the corresponding diradical species 1,4-[(E2N2C)C6H4(CN2E2)], which can be purified by high vacuum sublimation. The crystal structures of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are both monoclinic, space group P21/n. The crystal packing consists of sheets of interleaved columns of weakly associated diradical units (dimers); the mean intradimer separation is 3.34/3.37 {\AA} (E = S/Se), and the mean interdimer separation is 3.68/3.71 {\AA} (E = S/Se). The sulfur compound is an insulator, but the selenium material has a room temperature pressed pellet resistivity of about 100 fi cm. Magnetic susceptibility measurements show the solids to be predominantly diamagnetic with variable amounts of paramagnetic defects in the lattice. While the exact mechanism of conduction remains to be established, these systems represent the first structurally characterized conducting materials constructed from neutral molecular radicals. Extended Hiickel band structure calculations reveal band gaps of 0.84/0.69 eV (E = S, Se) for the crystalline solids. The calculated band dispersions show a high degree of three-dimensionality; to our knowledge these are the most isotropic organic molecular solids yet to be reported.",
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Molecular Semiconductors from Bifunctional Dithia- and Diselenadiazolyl Radicals. Preparation and Solid-State Structural and Electronic Properties of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se). / Cordes, A. Wallace; Haddon, Robert C.; Oakley, Richard T.; Schneemeyer, Lynn; Waszczak, Joseph V.; Young, Kelly M.; Zimmerman, Neil M.

In: Journal of the American Chemical Society, Vol. 113, No. 2, 01.01.1991, p. 582-588.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Molecular Semiconductors from Bifunctional Dithia- and Diselenadiazolyl Radicals. Preparation and Solid-State Structural and Electronic Properties of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se)

AU - Cordes, A. Wallace

AU - Haddon, Robert C.

AU - Oakley, Richard T.

AU - Schneemeyer, Lynn

AU - Waszczak, Joseph V.

AU - Young, Kelly M.

AU - Zimmerman, Neil M.

PY - 1991/1/1

Y1 - 1991/1/1

N2 - The reactions of 1,4-phenylenebis[N,N,N′-tris(trimethylsilyl)amidine] with sulfur and selenium dichlorides yield, respectively, the l,4-phenylenebis(dithiadiazolium) and bis(diselenadiazolium) dichlorides l,4-[(E2N2C)C6H4(CN2E2)]Cl2 (E = S, Se). Reduction of these materials with triphenylantimony affords the corresponding diradical species 1,4-[(E2N2C)C6H4(CN2E2)], which can be purified by high vacuum sublimation. The crystal structures of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are both monoclinic, space group P21/n. The crystal packing consists of sheets of interleaved columns of weakly associated diradical units (dimers); the mean intradimer separation is 3.34/3.37 Å (E = S/Se), and the mean interdimer separation is 3.68/3.71 Å (E = S/Se). The sulfur compound is an insulator, but the selenium material has a room temperature pressed pellet resistivity of about 100 fi cm. Magnetic susceptibility measurements show the solids to be predominantly diamagnetic with variable amounts of paramagnetic defects in the lattice. While the exact mechanism of conduction remains to be established, these systems represent the first structurally characterized conducting materials constructed from neutral molecular radicals. Extended Hiickel band structure calculations reveal band gaps of 0.84/0.69 eV (E = S, Se) for the crystalline solids. The calculated band dispersions show a high degree of three-dimensionality; to our knowledge these are the most isotropic organic molecular solids yet to be reported.

AB - The reactions of 1,4-phenylenebis[N,N,N′-tris(trimethylsilyl)amidine] with sulfur and selenium dichlorides yield, respectively, the l,4-phenylenebis(dithiadiazolium) and bis(diselenadiazolium) dichlorides l,4-[(E2N2C)C6H4(CN2E2)]Cl2 (E = S, Se). Reduction of these materials with triphenylantimony affords the corresponding diradical species 1,4-[(E2N2C)C6H4(CN2E2)], which can be purified by high vacuum sublimation. The crystal structures of 1,4-[(E2N2C)C6H4(CN2E2)] (E = S, Se) are both monoclinic, space group P21/n. The crystal packing consists of sheets of interleaved columns of weakly associated diradical units (dimers); the mean intradimer separation is 3.34/3.37 Å (E = S/Se), and the mean interdimer separation is 3.68/3.71 Å (E = S/Se). The sulfur compound is an insulator, but the selenium material has a room temperature pressed pellet resistivity of about 100 fi cm. Magnetic susceptibility measurements show the solids to be predominantly diamagnetic with variable amounts of paramagnetic defects in the lattice. While the exact mechanism of conduction remains to be established, these systems represent the first structurally characterized conducting materials constructed from neutral molecular radicals. Extended Hiickel band structure calculations reveal band gaps of 0.84/0.69 eV (E = S, Se) for the crystalline solids. The calculated band dispersions show a high degree of three-dimensionality; to our knowledge these are the most isotropic organic molecular solids yet to be reported.

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