Crystal Architectures and Magnetic Properties of Alkylferrocenium Salts with F_nTCNQ (n = 0, 2, 4): Effect of Substituents on the Self-Assembled Structures

Abstract

The crystal architecture and magnetic properties of the alkylferrocenium salts of tetracyanoquinodimethane (TCNQ) type acceptors have been investigated using 1,1′dimethyl-, 1,1′-diethyl-, 1,1′-diisopropyl-, tert-butyl-, and tert-pentyl-ferrocene as the donors. In all of the resulting salts, the donors and acceptors were stacked to form independent columns. The F4TCNQ salts had a D/A ratio of 1:1, and existed as hexagonal assembled structures composed of anion columns surrounded by cation columns. The F2TCNQ and TCNQ salts had a D/A ratio of 1:2, and existed as a rectangular arrangement of cation columns. Weak antiferromagnetic interactions were found to operate between the cations in these salts.

Improved Dynamic Properties of Charge-Transfer-Type Supramolecular Rotor Composed of Coronene and F4TCNQ

“…The nearly isotropic structure of coronene molecules in 2 is firm evidence of the absence of a Jahn–Teller distortion, namely, the neutral ground state. As for the charge state of the F 4 TCNQ molecule, the ratio of bond lengths, c /( b + d ) (see Figure b), is a diagnostic parameter for determining δ in the crystal, in view of the structural similarity between TCNQ and F 4 TCNQ. , The δ value in 2 , which was estimated to be −0.15(5) on the basis of a standard line through pristine F 4 TCNQ solid (δ = 0) and monoanionic F 4 TCNQ salts (δ = −1), − is in good agreement with that expected from the vibrational spectra described above. We note that the X-ray data at 298 K yield a δ value of −0.02(12), which is identical within the experimental error to that at 100 K.…”

Shape-Controlled Synthesis of Organometallic Microcrystal-Based Hollow Hexagonal Micromotors through Evaporation-Induced Supramolecular Self-Assembly

“…The crystal belongs to hexagonal system and the lattice parameters are as follows: a = b = 11.0094(3) Å, c = 28.1822(14) Å, α = β = 90°, γ = 120° (Figure a,b). The single crystal X-ray diffraction analysis results imply that the major interactions among adjacent molecules are π–π stacking and intermolecular hydrogen bonds (Figure d). , The crystal models were used to explain clearly why a certain plane was more energetic than the others. Along the direction of the a -axis or b -axis, the same direction of (100) and (010) planes, respectively, ferrocenoyl moieties interact with ambient benzocyclohutene through strong π–π stacking interactions (Figure and the cycle 1 in Figure d).…”

Gram-Scale Synthesis of 2,5-Difluoro-7,7,8,8-tetracyanoquinodimethane (F2-TCNQ)

“…Among the members of the F n -TCNQ family, F 2 -TCNQ also has a unique stacking in a single crystal structure. − The unique face-to-face crystal stacking of F 2 -TCNQ is thought to account for its phenomenal electron mobility relative to TCNQ and F 4 -TCNQ. Finally, the properties of the F n -TCNQ family have been investigated as complexes, − co-crystals, − and adducts with various metal ions and other materials. − …”