Charge-transfer salts of branched-alkyl biferrocenes, (1',1' ''-R2-1,1' '-biferrocene)[Ni(mnt)2] (1a, R = isopropyl; 2a, R = dineopentyl) and (1',1' ''-R2-1,1' '-biferrocene)2[Co(mnt)2]2 (1b, R = isopropyl; 2b, R = dineopentyl), were prepared. Their valence states were investigated using X-ray crystallography and Mössbauer spectroscopy. Complexes 1a and 1b show segregated-stack crystal structures that contain columns of acceptors, whereas structures of 2a and 2b, which contain bulky donors, are rather discrete. All of the complexes contain mixed-valent biferrocenium monocations. A two-step valence transition was found in complex 1a. The crystal contains two crystallographically independent cations: one undergoes valence localization below room temperature; the other undergoes valence localization below ca. 130 K. The former transition is derived from asymmetry of the crystal environment around the cation, whereas the latter one is caused by symmetry lowering coupled with a spin-Peierls transition (T(C) = 133.2 K) associated with the dimerization of the acceptors. This compound was found to exhibit a dielectric response based on valence tautomerization. Other complexes (1b, 2a, and 2b) show a valence-trapped state. In all complexes, charge localization was found to occur through local electrostatic interactions between the donor's cationic moiety and the acceptor's electronegative moieties.

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An ionic molecular crystal of (1',1'''-dineopentylbiferrocene)(F1TCNQ)3 exhibits a first-order phase transition from a monovalent state (D(+)A3(-)) to a divalent state (D(2+)A3(2-)) at around 120 K. The transition was successfully controlled by modulation of the redox potentials using FnTCNQ (n = 0-2) and by chemical-pressure effects.

In the title compound, (C(16)H(36)N)(2)[Co(C(4)N(2)S(2))(2)](2), pairs of [Co(C(4)N(2)S(2))(2)](-) anions combine to form discrete crystallographically centrosymmetric dimers, which stack along the c axis, surrounded by the counter-cations. The metal atom in the anion has a five-coordinate distorted square-pyramidal geometry.