Triethylphosphine as a molecular gear - phase transitions in ferrocenyl-acetylide-gold(I)

A sequence of two discontinuous phase transitions, occurring just above 125 K and 148 K, has been observed for a ferrocenyl-acetylide-gold(I) complex with triethylphosphine, structure (1), by means of a multi-temperature single-crystal X-ray diffraction technique. Three distinct phases have been identified. The high-temperature α and low-temperature γ phases share the same space group Pbca, whereas the intermediate β phase is in the Pb2₁a subgroup of Pbca. In all phases molecules of (1) form well defined double layers, with PEt₃ groups interlocking in planes perpendicular to c. On the molecular level, both phase transitions involve almost uniquely a conformational change of triethylphosphine: a gear-like rotation around the P-Au axis and concerted flips of the ethyl moieties. The mechanism of these transitions may be imagined as initiated by a rotation of a single PEt₃ group in a double layer (a single gear movement), followed by adjacent phosphines adjusting their conformations as a result of steric strain. The structural changes underlying phase transitions are sequential, occurring layer-wise, the γ→β transition involving approximately every other layer in the crystal lattice, the β→α yielding a total conformation change. The sequence of phase transitions results in a noticeable contraction of the crystal cell volume.