Variable-Rung Design for a Mixed-Valence Two-Legged Ladder System Situated in a Dimensional Crossover Region.

Ladder systems situated in a crossover from one dimensionality to two dimensionalities have been an attractive research target, because the physical properties, which are associated with dimensionality, are strongly dependent on the number of constituent legs. However, control of the intraladder configuration and electronic properties based on the substitution of structural components remain challenging tasks in materials science. On the other hand, structural design using coordination chemistry offers crucial advantages for architectural and electronic variations through substitutions of metal--organic building blocks. Here, we show the rational design and electronic properties of novel metal complex-based two-legged ladder compounds with several organic rung units: 4,4'-bipyridine, trans-1,4-diaminocyclohex-ane, and 4,4'-azopyridine. Single-crystal X-ray studies show that these two-legged ladder compounds are composed of halogen-bridged mixed-valence one-dimensional chains (MX chains) as their constituent legs. Depending on the molecular shape of the organic rung units, unique configurations of two-legged ladder lattices with periodic distortion of the legs are achieved. In addition, the electronic absorption spectra show that intervalence charge-transfer (IVCT) band gap of the two-legged ladder system increases with increasing degree of distortion of the leg. We have demonstrated for the first time that a two-legged ladder system shows a unique relationship between IVCT energy and the distortion parameter of the leg, as distinct from a single MX chain system. These systematic investigations, not only of configurations based on the rung variation but also of electronic states in metal--organic ladder system, provide the possibility for wide and rational tunings of physical and electronic properties of metal complex-based functional materials. [ABSTRACT FROM AUTHOR]