The possibilities of new metal-mesogenic complex formation and their solid phase chemical reactions have been demonstrated using low temperature co-condensation techniques and ESR-spectroscopy for a solid triple system, containing silver, the mesogenic ligand 4-pentyl-4-cyanobiphenyl (5CB) and an alternative electron-acceptor ligand or the third reactive component carbon tetrachloride (CCl4). It was shown by ESR-spectroscopy that the existence of four paramagnetic products were stabilised in the system at low temperatures: silver atom n-complex with two cyanobiphenyl molecules, silver atom a-complex with cyanobiphenyl molecule stabilised by CCl4 co-ligand, AgCl- CCl(3)center dot and silver nanoclusters, formed by silver atom aggregation in the mesogenic matrix. The relative thermal stability of these silver species and their thermal behavior are discussed.