Abstract The present thesis has been developed between the frontiers of different disciplines such as Coordination and Supramolecular Chemistry and Material Science. The main objective has been the design and construction of nano-supramolecular gate-ensemble, which can be defined as a basis device that modulate the access to a certain site and whose state (opened or closed) can be controlled at will by certain external stimuli, for example ionically, electrochemically and photochemically. One of the most important ideas of this thesis is the development of molecular gates using organic-inorganic hybrid systems. We have been working with a mesoporous siliceous matrix MCM-41 type and UVM-7 that possesses preorganized cavities, in that sense the porous system are homogeneous in size even in shape and periodicity. Furthermore, it has been possible to obtain systems highly functionalized due to its high specific surfaces areas (internal and external). First of all, it has been studying the design of ionically-controlled nanoscópico molecular gates. The idealized open-closed mechanism would arise from simple interactions between amines (open-gate) and Coulombic repulsion between ammonium groups (closed-gate).When protonated the open-chain polyamines in the external surface would adopt a rigid-like conformation and would be pushed away towards the pore openings due to repulsion between ammonium groups charged positively. A fundamental aspect related to molecular gates was the demonstration of specific functions like “open-close” could be controlled wilfully by certain external stimuli. In this sense, we used two different approximations to prove how works the molecular machine: a) detect the access (controlled by external stimuli) to the pores of certain species in solution and b) study the release of some molecules entrapped from the pore voids into the bulk solution. The first approximation, the most difficult to control, has been carried out by using a coupled reaction that would give one observable and easy signal such as change of colour and even more the only way to occur was if the studied species came inside the nanometric porous. In second place it was reported a complete study of the behaviour of a pH-driven and anion-controlled nano-supramolecular gate-like ensemble obtained by anchoring suitable polyamines on the pore outlets of mesoporous materials of the type MCM-41. The release of an entrapped dye (Ru(bipy)32+) from the pore voids into the bulk solution allows us to study the gating effect. This study was carried out by monitoring the dye released from the pore voids of the solid at a certain pH in the presence of a range of anions with different structural dimensions and charges, including chloride, sulphate, phosphate, and ATP. The choice of a certain anionic guest results in a different gate-like ensemble behaviour, ranging from basically no action (chloride) to complete (ATP) or partial pore blockage, depending on the pH (sulphate and phosphate).Molecular dynamics simulations using force field methods have been carried out to explain the pH-driven open/close mechanism and selectivity patterns have been discussed in terms of kinetic rates of the liberation of the dye. Furthermore, it has been applied the potential use of molecular gatelike systems as a new strategy for the chromogenic signalling of the target anions in aqueous solutions. The idea involves molecular-recognition events coupled with the control of dye transport. It entails the use of solids with nanoscopic 3D organized surfaces (mesoporous solids) that have been functionalized at the outer surface with certain binding moieties (for example amines) and additionally the pores have been loaded with a suitable dye. In absence of any species to detect there is an opened gatelike system that is able to deliver the enclosed dye to the solution. The addition of a target anionic guest capable of forming a suitable complex with the binding site might “close the gate” which would lead to recognition, thus signalling the target anion by the inhibition of the mass-delivery process. In this work we have confirmed the ATP recognition and signalling by inhibiting dye release with nanoscópico supramolecular gatelike systems on mesoporous MCM-41 supports. Finally, a dual functional hybrid material was designed for the simultaneous chromo-fluorogenic detection and removal of Hg2+ in aqueous environment. The mesoporous solid is functionalized with thiol groups that have been further reacted with the squaraine dye, resulting in the formation of a 2,4-bis(4-dialkylaminophenyl)-3-hydroxy-4-alkylsulfanylcyclobut-2-enone (PAS) derivative being anchored to the inorganic silica matrix. When the species to detect, the Hg2+ cation, is present in the solution this reacts with the PAS fragment in the solid, releasing the squaraine dye to the solution that turned deep blue and highly fluorescent. This allows a straightforward “naked-eye” detection of Hg2+ employing an easy-to-use procedure.