[2.2]‐ and [3.3]Tetrathiafulvalenophanes

Abstract

In the “metallic” conducting 1:1 complex of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ), donor and acceptor molecules form separate stacks in the crystal. In order to enforce other TTF/TCNQ arrangements by altering the molecular architecture the phane‐like bridged TTF‐paracyclophanes (1), n = 3, and (2) were first synthesized. To do this a novel reaction sequence had to be developed which also facilitated synthesis of the tetrathiafulvalenophanes (3)/(4) (and the corresponding [2.2]‐derivatives). (3)/(4) and TCNQ form a 1:4 complex having a conductivity of σ = 5 × 10−3 to 10−2 [Ω cm]−1 (single crystal, long axis, 300 K).

Bi-TTF, Bis-TTF, and Related TTF Oligomers

“…The first examples of cyclophane-type bis-TTFs 142 were reported by Staab in 1980 116a. The structure of 142a was determined by X-ray analysis.…”

“…This result suggests that 142a has a steplike anti conformation. Although 143 with longer double bridges was synthesized, no information on its structure was described 116b …”

Stable Macrocyclic and Tethered Donor−Acceptor Systems. Intramolecular Bipyridinium and Tetrathiafulvalene Assemblies

“…In the previous examples, the right geometry and connection of the donor portion are essential for intramolecular interactions. Macrocyclic systems containing two TTF units have also been prepared . Cyclophanes containing two electron acceptors derived from 4,4‘-bipyridinium dication 2 have been synthesized by Hünig et al, and their intra and intermolecular interactions were extensively investigated .…”

Syntheses, Unique Strained Molecular Structures, and Unusual Transannular Electronic Interactions of a Series of Crisscross-Overlapped Tetrathiafulvalenophanes

“…Of a number of such compounds ever designed, tetrathiafulvalenophanes (TTF phanes), in which the two TTF units are stacked by two or more spacer bridges, are of particular interest, because they have unique nonplanar, double-layered structures, which might form molecular complexes different in crystal structure and solid properties from the usual ones based on the ordinary planar TTF donors. Until quite recently, however, only few examples of TTF phanes were known and quadruple-bridged one 5 , of which the former gave highly conductive molecular complexes.…”