Molecular Deformation, Charge Flow, and Spongelike Behavior in Anion-π {[M(CN) ] ;[HAT(CN) ]} (M=Ni, Pd, Pt) Supramolecular Stacks.

The synthesis, crystal structures, spectroscopic characterization, and comprehensive quantum-chemical calculations for a novel series of anion-π hybrid salts (XPh ) [M(CN) ][HAT(CN) ]⋅3 MeCN (X=P, M=Ni (1), Pd (3), Pt (5); X=As, M=Ni (2), Pd (4), Pt (6); HAT(CN) =1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) are presented. The systems comprise 1D {[M(CN) ] ;[HAT(CN) ]} stacks, in which the electron-rich metal complexes adjust their orientation to match the electron-deficient areas of HAT(CN) . Electronic charge-transfer interactions along the stacks result in polarization of electron density within HAT(CN) and in perturbations along the {[M(CN) ] ;[HAT(CN) ]} contacts.