Molecular conductors with 8,8′-diiodo cobalt bis(dicarbollide) anion

Kazheva, Olga N.; Alexandrov, Grigorii G.; Кравченко, А. В.; Стародуб, В. А.; Lobanova, I. A.; Sivaev, Igor B.; Bregadze, V. I.; Titov, L. V.; Buravov, L. I.; D’yachenko, O. A.

doi:10.1016/j.jorganchem.2009.03.035

Cited by 49 publications

(27 citation statements)

References 31 publications

(29 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The distance from the Co atom to the C 2 B 3 plane is 1.46 Å, which is somewhat shorter than the corresponding distances in compounds 5 15 The electrophysical measurements showed that at room temperature, salt 6 has semiconductor properties with σ 293 = 6•10 -7 Ohm -1 cm -1 , which is somewhat larger than that in the related salt with the unsubstituted anion (TTF)[3,3´ Co(1,2 C 2 B 9 H 11 ) 2 ] 5 but is five orders of magnitude smaller than the conductivity of the salt (TTF)[8,8´ I 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ]. 8 The temperature dependence log[R(T)/R(293 K)] = f(T -1 ) in the 220-293 K temperature range has an activation character with the activation energy E a ≅ 0.24 eV.…”

Section: Methodsmentioning

confidence: 99%

“…3,4 Previously, we have investigated the influence of various substituents in the cobalt bis(dicarbollide) deriva tives [8,8´ X 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] -(X = H, Br, or I) on the crystal structures and the conductivities of molecu lar conductors based on radical cation salts of tetrathiaful valene and its derivatives. [5][6][7][8] The aim of the present study was to synthesize and investigate radical cation salts with cobalt bis(dicarbollide) derivatives containing substituents in the lower rim of the dicarbollide ligand, viz., [9,9´(12´) I 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] -and [9,9´,12,12´ I 4 3,3´ Co(1,2 C 2 B 9 H 9 ) 2 ] -.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, structures, and conductivities of salts (BEDT-TTF)[9,9′(12′)-I2-3,3′-Co(1,2-C2B9H10)2] and (TTF)[9,9′,12,12′-I4-3,3′-Co(1,2-C2B9H9)2]

et al. 2010

View full text Add to dashboard Cite

The radical cation salts of tetrathiafulvalene (TTF) and bis(ethylenedithio)tetrathiafulvalene (BEDT TTF) with iodo derivatives of cobalt bis(dicarbollide), (TTF)[9,9´,12,12´ I 4 3,3´ Co(1,2 C 2 B 9 H 9 ) 2 ] and (BEDT TTF)[9,9´(12´) I 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ], respectively, were synthesized and their crystal structures were determined. The introduction of iodine atoms into the lower rim of the dicarbollide ligands, unlike the substitution at the upper rim, leads to insignificant changes in the crystal structure and the conductivity of the radical cation salts compared to the analogous salts based on unsubstituted cobalt bis(dicarbollide).One of challenges of science and engineering is the design of new materials having combined properties. Mo lecular conductors traditionally occupy an important place among these materials. Nowadays, radical cation salts based on organic π donors belong to the main class of molecular conductors. These compounds are of great in terest because of the diversity of structural types and pos sibilities of varying the transport properties in a wide range. These quasi two dimensional systems have layered struc tures characterized by the presence of conducting radical cation layers alternating with anion layers. The cation and anion layers are spatially well separated in the crystal struc tures and form two sublattices. The conduction band is formed by the highest occupied molecular orbitals of radi cal cations. The anions that separate the radical cation layers have an effect on the packing mode of the donor molecules, which is responsible for the character of the transport properties. As a rule, the anions are not directly involved in the conduction process but, having specific properties (magnetic, photochromic, nonlinear optical, etc.), can be responsible for the corresponding physical properties of the crystals. 1,2The complementarity between organic and inorganic layers is of importance for the crystal formation of radical cation salts. The difference in the translation parameters of the sublattices can lead to the formation of both com mensurate and incommensurate structural modulations. In the presence of the same donor, conductors having different structural and physical properties can be pre pared by varying the composition of the anion sublattice.The bis(dicarbollide) complexes of iron subgroup met als [3,3´ M(1,2 C 2 B 9 H 11 ) 2 ] -(M = Fe, Co, and Ni) be long to a promising class of compounds for the design of molecular conductors due to their high stability, the pos sibility of varying the charge and the nature of the metal in * Dedicated to Academician of the Russian Academy of Sciences I. L. Eremenko on the occasion of his 60th birthday.

show abstract

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Synthesis, structures, and conductivities of salts (BEDT-TTF)[9,9′(12′)-I2-3,3′-Co(1,2-C2B9H10)2] and (TTF)[9,9′,12,12′-I4-3,3′-Co(1,2-C2B9H9)2]

et al. 2010

View full text Add to dashboard Cite

show abstract

“…9) and by eight times higher than that for iodine containing analog 6 (see Ref. 10). As in the case of salt 1, an increase in the electroconductivity can be due to the compacting of the radical cation packing with a decrease in the substitu ent size in the dicarbollide ligand.…”

Section: Resultsmentioning

confidence: 84%

“…3- 6 We have previously studied the influence of different substituents in the derivatives of cobalt bis(1,2 di carbollide) [8,8´ X 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] -(X = H, Br, I) on the crystal structure and conductivity of molecu lar conductors based on radical cation salts of tetrathiaful valene and its derivatives. [7][8][9][10] This work is devoted to the synthesis and study of the structure and conducting properties of radical cation salts (BEDT TTF) 2 [8,8´ Cl 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (1) and (BMDT TTF) 4 [8,8´ Cl 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (2).…”

mentioning

confidence: 99%

Syntheses, structures, and electroconductivity of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and bis(methylenedithio)tetrathiafulvalene (BMDT-TTF) salts with cobalt 8,8′-dichloro-3,3′-bis(1,2-dicarbollide)

et al. 2014

View full text Add to dashboard Cite

Radical cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT TTF) and bis(methyl enedithio)tetrathiafulvalene (BMDT TTF) with the 8,8´ dichloro derivative of cobalt bis(1,2 dicarbollide) (BEDT TTF) 2 [8,8´ Cl 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (1) and (BMDT TTF) 4 [8,8´ Cl 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (2) were synthesized and their crystal structures and electrocon ducting properties were determined. The synthesized radical cation salts are semiconduc tors with the conductivity  293 = 1.5 and 2.0 Ohm -1 cm -1 , respectively. A decrease in the size of the substituent in a series of (BEDT TTF) 2 [8,8´ X 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] and (BMDT TTF) 4 [8,8´ X 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (X = I, Br, Cl) results in the compression of the anion sublattice of the crystal and compaction of the radical cation packing of the conduct ing layer, which, in turn, increases the conductivity of the crystals.The main class of molecular conductors is radical cat ion salts, whose structure is characterized by conducting piles or layers of organic  electron donors separated by inorganic (organometallic) anions. Depending on the packing of radical cations, crystals of molecular organic conductors can possess the very different electroconduct ing properties: from dielectric to metallic and super conducting. As a rule, anions are not directly involved in the conduction process; however, their nature (shape, size, and charge) can substantially affect the packing of radical cations in the conducting layers and, correspondingly, the conductivity of the crystal. 1,2 Bis(dicarbollide) complexes of transition metals of the iron group [3,3´ M(1,2 C 2 B 9 H 11 ) 2 ] -(M = Fe, Co, Ni) represent a promising class of compounds for the prepara tion of molecular conductors due to their high stability, a wide possibility of varying the charge and nature of the metal, and the possibility to modify the initial bis (dicarbollide) by the directed introduction of various sub stituents. 3-6 We have previously studied the influence of different substituents in the derivatives of cobalt bis(1,2 di carbollide) [8,8´ X 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] -(X = H, Br, I) on the crystal structure and conductivity of molecu lar conductors based on radical cation salts of tetrathiaful valene and its derivatives. 7-10 This work is devoted to the synthesis and study of the structure and conducting properties of radical cation salts (BEDT TTF) 2 [8,8´ Cl 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (1) and (BMDT TTF) 4 [8,8´ Cl 2 3,3´ Co(1,2 C 2 B 9 H 10 ) 2 ] (2). Results and DiscussionBis(dicarbollide) complexes of transition metals [3,3´ M(1,2 C 2 B 9 H 11 ) 2 ] -are of significant interest as counteri ons for the preparation of molecular conductors based on

show abstract

“…Recently we studied the effect of iodo- [9][10][11], bromo- [12] and hydroxy- [13] substituents in cobalt bis(1,2-dicarbollide) complexes on crystal packing and physical properties of their salts with TTFbased radical cations. In this paper, we report the crystal structures and electrical conductivities of tetrathiafulvalenium salts of dichloro and mixed bromo-chloro and bromo-hydroxy derivatives of cobalt bis(dicarbollide) anion.…”

Section: Introductionmentioning

confidence: 99%

New Fulvalenium Salts of Cobalt Bis(dicarbollide): Crystal Structures and Electrical Conductivities

et al. 2012

Self Cite

View full text Add to dashboard Cite

New radical cation salts (BEDT-TTF) [8,8',(7)-Cl 2 (Cl 0.09 )-3,3'-Co(1,2-C 2 B 9 H 9.91 )(1',2'-C 2 B 9 H 10 )] (1), (BEDT-TTF) [8, Cl 1.25 -3,3'-Co(1,2-C 2 B 9 H 10 ) 2 ] (2), and (BMDT-TTF) 4 [8, (OH) 0.72 -3,3'-Co(1,2-C 2 B 9 H 10.06 ) 2 ] (3) were synthesized, and their crystal structures and electrical conductivities were determined. All the radical cation salts are semiconductors. Compounds 1 and 2 were found to be isostructural, however their electrical conductivities strongly differ ( 293 = 2 Ω , respectively).

show abstract

Molecular conductors with 8,8′-diiodo cobalt bis(dicarbollide) anion

Cited by 49 publications

References 31 publications

Synthesis, structures, and conductivities of salts (BEDT-TTF)[9,9′(12′)-I2-3,3′-Co(1,2-C2B9H10)2] and (TTF)[9,9′,12,12′-I4-3,3′-Co(1,2-C2B9H9)2]

Synthesis, structures, and conductivities of salts (BEDT-TTF)[9,9′(12′)-I2-3,3′-Co(1,2-C2B9H10)2] and (TTF)[9,9′,12,12′-I4-3,3′-Co(1,2-C2B9H9)2]

Syntheses, structures, and electroconductivity of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and bis(methylenedithio)tetrathiafulvalene (BMDT-TTF) salts with cobalt 8,8′-dichloro-3,3′-bis(1,2-dicarbollide)

New Fulvalenium Salts of Cobalt Bis(dicarbollide): Crystal Structures and Electrical Conductivities

Contact Info

Product

Resources

About