Mesogenic nanosystems including silver and copper, and long-chain alkylcyanobiphenyls (CB) and alkylcyanophenylpyridines (PPy) have been obtained by low-temperature vacuum co-condensation of reagent vapors on cooled support surfaces. The formation of metastable bi-ligand pi-complexes of metal atoms and small clusters during co-condensation at low temperatures have been shown by FTIR, ESR and UV-Vis spectroscopy combining with the results of quantum chemistry calculations at HF/MP2 and DFT/B3LYP levels. Controlled thermal treatment of co-condensate samples allowed the directed formation of metal nanoparticles of definite size from 2 up to 100 nm. Formation of silver nanoclusters was also caused by UV-irradiation of co-condensate films.