Molecular Complexes of Cyclophanes, Part XVI On the Donor Properties of Polynuclear Paracyclophanes and their Sulfur Analogues

Mourad, Aboul-Fetouh E.; Hucker, Joachim; Hopf, Henning

doi:10.1515/znb-1987-0914

Cited by 6 publications

(1 citation statement)

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“…The CT interactions between [2 2 ]CPs and TCNQ or TCNE in solution were studied by Mourad et al However, only a limited number of papers on the solid-state structural study of the CT complexes of the cyclophanes have been reported. Trueblood et al reported the crystal structure of the 1:1 complex of [3 2 ](1,4)CP with TCNE .…”

Section: Introductionmentioning

confidence: 99%

An Alternative Synthetic Route of [3₅](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3_n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State¹

et al. 2002

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To develop an improved synthetic route to [3(6)](1,2,3,4,5,6)cyclophane (CP) 2, a more practical synthetic route to [3(5)](1,2,3,4,5)CP 3 than the original one was developed, which started from [3(2)](1,3)CP 7 via [3(4)](1,2,4,5)CP 5. The fundamental structural parameters of [3(n)]CPs (n = 3-6) in the solid state were elucidated, and the observed structures were in good agreement with the most stable conformers in solution and those predicted by the theoretical calculations. In the case of [3(6)]CP 2, the most stable C(6)(h) structure was observed in the crystal structure of the 2-TCNQ-F(4) (1:1) complex, whereas the highly strained structure with a D(6)(h) symmetry was observed in the crystal structure of 2 and the 2:TCNQ:benzene (1:1:1) complex because of a severe disorder problem. [3(n)]CPs (n > 3) showed reversible redox processes, and 2 (+0.39 V vs F(c)/F(c)(+), Cl(2)CHCHCl(2)) showed the lowest first half-wave oxidation potential [E(1/2) (I)] in [3(n)]CPs. The E(1/2) (I) data support the strong donating ability of 2 and its lower homologues. This is attributed to their molecular structures where effective hyperconjugation between the benzyl hydrogens and benzene ring is possible. By taking advantage of the strong electron-donating ability of [3(n)]CPs, their CT complexes with TCNE, TCNQ, and TCNQ-F(4) were prepared, and their crystal structural properties were examined. The single-crystal conductivity data of the CT complexes indicated that the TCNQ-F(4) complexes showed higher conductivities than the corresponding TCNQ complexes mainly due to a larger charge separation. Among the [3(n)]CP-TCNQ complexes, the [3(3)](1,3,5)CP 6-TCNQ-F(4) (1:1) complex showed the highest conductivity (10(-)(4) S cm(-)(1)), and this was ascribed to the formation of an infinite column of partially overlapped acceptors with a short acceptor-acceptor distance, while the formation of such a column was not observed in the 2-TCNQ-F(4) complex. Although the conductivities of the cyclophane-CT complexes are much lower than those of the TTF related complexes, this study successfully provides the basic knowledge for understanding the CT interactions in the solid state.

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Section: Introductionmentioning

confidence: 99%

An Alternative Synthetic Route of [3₅](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3_n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State¹

et al. 2002

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New Access to the Chemistry of Piperonylidinyl‐4‐[2.2]‐Paracyclophanylamine and Some Electron π‐Deficients

El‐Shaieb

2004

J Chinese Chemical Soc

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Thiophenes and their Benzo Derivatives: Applications

Russell¹

1996

Comprehensive Heterocyclic Chemistry II

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Molecular Complexes of Cyclophanes, Part XVI On the Donor Properties of Polynuclear Paracyclophanes and their Sulfur Analogues

Cited by 6 publications

References 9 publications

An Alternative Synthetic Route of [3₅](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3_n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State¹

An Alternative Synthetic Route of [3₅](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3_n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State¹

New Access to the Chemistry of Piperonylidinyl‐4‐[2.2]‐Paracyclophanylamine and Some Electron π‐Deficients

Thiophenes and their Benzo Derivatives: Applications

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Molecular Complexes of Cyclophanes, Part XVI On the Donor Properties of Polynuclear Paracyclophanes and their Sulfur Analogues

Cited by 6 publications

References 9 publications

An Alternative Synthetic Route of [35](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State1

An Alternative Synthetic Route of [35](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State1

New Access to the Chemistry of Piperonylidinyl‐4‐[2.2]‐Paracyclophanylamine and Some Electron π‐Deficients

Thiophenes and their Benzo Derivatives: Applications

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An Alternative Synthetic Route of [3₅](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3_n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State¹

An Alternative Synthetic Route of [3₅](1,2,3,4,5)Cyclophane, and Structural Properties of Multibridged [3_n]Cyclophanes and Their Charge-Transfer Complexes in the Solid State¹