The possibilities of new metal-mesogenic complexes formation and their solid phase chemical reactions have been demonstrated using low temperature co-condensation technique and ESR-spectroscopy for solid triple system, containing silver, mesogenic ligand 4-pentyl-4-cyanobiphenyl (5CB) and 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 are stabilized in the system at low temperatures: silver atom pi-complex with two cyanobiphenyl molecules, silver atom sigma-complex with cyanobiphenyl molecule stabilized by CCl4 co-ligand, complex of AgCl molecule with trichloromethyl radical - AgCl center dot CCl3center dot and silver nanoclusters - Ag-x, formed by silver atoms aggregation in mesogenic matrix. The relative thermal stability of these silver species and mechanism of their thermal behavior are discussed. (c) 2004 Published by Elsevier B.V.