Proton-driven self-assembled systems based on cyclam-cored dendrimers and [Ru(bpy)(CN)4]2-

1,4,8,11-Tetraazacyclotetradecane (cyclam), which is one of the most extensively investigated ligands in coordination chemistry, in its protonated forms, can play the role of host toward cyanide metal complexes. We have investigated the acid-driven adducts formed in acetonitrile-dichloromethane (1:1 v/v) solution by [Ru(bpy)(CN)(4)](2)- with 1,4,8,11-tetrakis(naphthylmethyl)cyclam (1) and a dendrimer consisting of a cyclam core appended with 12 dimethoxybenzene and 16 naphthyl units (2). [Ru(bpy)(CN)4]2-, 1, and 2 exhibit characteristic absorption and emission bands, in distinct spectral regions, that are strongly affected by addition of acid. When a solution containing equimolar amounts of [Ru(bpy)(CN)(4)](2-) and 1 or 2 is titrated by trifluoroacetic acid, or when [Ru(bpy)(CN)(4)](2-) is titrated with (1(.)2H)(2+) or (2(.)2H)(2+), {[Ru(bpy)(CN)(4)](2-) (.)(2H(+))(.)1} or {[Ru(bpy)(CN)(4)](2-) (.)(2H(+))(.)2} adducts are formed in which the fluorescence of the naphthyl units is strongly quenched by very efficient energy transfer to the metal complex, as shown by the sensitized luminescence of the latter. The {[Ru(bpy)(CN)(4)](2-) (.)(2H(+))(.)1} and {[Ru(bpy)(CN)(4)](2-) (.)(2H(+))(.)2} adducts can be disrupted (i) by addition of a base (1,4-diazabicyclo[2.2.2]octane), yielding the starting species [Ru(bpy)(CN)(4)](2-) and 1 or 2, or (ii) by further addition of triflic acid, with formation of (1(.)2H)(2+) or (2-2H)(2+) and protonated forms of [Ru(bpy)(CN)(4)](2-). It is shown that upon stimulation with two chemical inputs (acid and base) both {[Ru(bpy)(CN)(4)](2-.)(2H(+))(.)1} and {[Ru(bpy)(CN)(4)](2-.)(2H(+))(.)2} exhibit two distinct optical outputs (a naphthalene-based and a Ru(bpy)-based emission) that behave according to an XOR and an XNOR logic, respectively.