Memory devices based on novel alkyl viologen halobismuthate(iii) complexes.

Four novel halobismuthate(iii) complexes with alkyl viologen cations: (R2Viol)2[Bi2X10] (R = n-butyl, n-pentyl, X = Cl, Br) have been synthesized. Both chloride complexes revealed photochromic behavior and were successfully utilized for the fabrication of OFET-based memory devices with high switching coefficients and good write-read-erase cycling stability.

Bromine-rich complexes of bismuth: experimental and theoretical studies.

Three novel polybromide complexes of bismuth(iii) - (2,6-MePyH)3[BiBr5(Br3)] (1), (H2bpp){[BiBr5](Br2)} (2) and (3-ClPyH)2{[BiBr5](Br2)} (3) - were synthesized. The results of an extended screening involving a set of organic cations resulting in the formation/non-formation of Bi(iii) polybromides are presented and discussed. The nature of BrBr interactions in Bi(iii) polybromides was investigated by theoretical methods, enabling the estimation of their energies.

Halogen Contacts-Induced Unusual Coloring in BiIII Bromide Complex: Anion-to-Cation Charge Transfer via Br⋠⋠⋠Br Interactions.

A yellow bromobismuthate {(2-BrPy)2 H}[BiBr4 ] (1, 2-BrPy=2-bromopyridinium) transforms into the unusually deeply colored cherry-red (2-BrPyH)2 [BiBr5 ] (2). A combination of structural studies and theoretical calculations confirms that the appearance of short non-covalent Br⋅⋅⋅Br interactions (≈3.3 Å) in 2 is responsible for the anion-to-cation charge transfer (LP(Brligand )→σ*(Br-C)), yielding dramatic changes in optical behavior. This effect opens the way towards novel halogen bonding-templated halometalate-based hybrid materials with enhanced optical properties.

Bi(iii) polybromides: a new chapter in coordination chemistry of bismuth.

A new family of bismuth coordination compounds - Bi(iii) polybromides - is introduced. Four representatives of this class - (N-EtPy)3[Bi2Br9](Br2)2 (1), (4-MePyH)3[Bi2Br9](Br2) (2), (H2bpe){[BiBr5]}(Br2) (3) and (BPB)2[BiBr5(Br3)](Br3)(Br2) (4) - were obtained in a simple way from HBr solutions of BiBr3 with added Br2, highlighting the diversity of the structural types in the new family of complexes.