The stability of the antitumor Ru(III) complex (H(2)trz)[trans-RuCl4(N-2-Htrz)(2)] within a tailored sol-gel silica matrix was studied, combining the information from UV-vis and infrared spectroscopies. The matrix was synthesized by a one-step sol-gel process catalyzed by hydrofluoric acid, resulting extremely light, hydrophobic and fluorinated. It is shown that upon encapsulation, the complex undergoes a series of processes, starting with the increase in charge density on the metal center, followed by hydrolysis reactions. The modified complex interacts with the matrix through hydrogen bonds between the aquo/hydroxo ligands and the fluorine atoms. Its interactions with DNA purines (guanine and adenine) were probed within the confined medium defined by the same silica matrix. It is found that coencapsulated guanine does not interfere with the complex aquation processes, while coencapsulated adenine has a delaying effect. No covalent bonding between the complex and the purines is detected, but interactions between the triazole ligands and the imidazole ring of guanine and the imidazole and pyrimidine rings of adenine are observed. Hydrogen bonding is established between the carbonyl and the ammine groups of guanine and the aquo/hydroxo ligands of the complex. For adenine, those interactions involve mostly the N9H of the purine and the NH groups of the triazole ligands, in addition to pi-pi interactions.