Designed solvent-free approach toward organometallic networks built on directional metal–π-arene interactions

This work overviews our recent results on application of the gas phase deposition approach toward controlled formation of novel solid organometallic networks. Volatile electrophilic dimetal complexes of Rh(II), Ru(II), and Ru(I) and various organic π-donors have been used as complementary building blocks in co-deposition reactions. The selected ligands range from hydrocarbons having isolated π-bonds and aromatic rings to conjugated polyarenes with planar or curved unsaturated carbon surfaces. The selected dimetal core complexes have a strong avidity for axial coordination and function as linear spacers in organometallic assembling reactions. Co-deposition of the above blocks in a solvent-free environment results in the controlled assembling of crystalline organometallic products. The technique is very effective in differentiation of π-bonding sites of multifunctional ligands and in utilization of directional metal–π-arene interactions for the construction of extended frameworks.