The monometallic complexes [(bpy)2Ru(tpphz)]2+ (4) and [(bpy)2Os(tpphz)]2+ (5), where tpphz is the poorly soluble fully aromatic tetrapyrido[3,2-a:2‘,3‘-c:3‘‘,2‘‘-h:2‘‘‘,3‘‘‘-j]phenazine, have been obtained by reaction of 5,6-diamino-1,10-phenanthroline with [(bpy)2M(phendione)]2+ (M = RuII or OsII). Reaction of 4 and 5 with metallic precursors yielded the homo- and heterobimetallic complexes [(bpy)2Ru(tpphz)Ru(NH3)4]4+ (6), [(bpy)2Ru(tpphz)Ru(bpy)2]4+ (7), [(bpy)2Os(tpphz)Os(bpy)2]4+ (8), and [(bpy)2Ru(tpphz)Os(bpy)2]4+ (9). The mononuclear 4 and 5 aggregate in solution, probably by π−π stacking of the tpphz part as shown from proton NMR. The complexes show one reversible metal-centered oxidation and several reversible (except 6) reductions which add one electron on the tpphz ligand, one electron on one bpy of each metallic end, a second electron on one bpy of each metallic end, and then a second electron on the tpphz ligand. The complexes (except 8) are luminescent in acetonitrile. Quenching of the luminescence by water has been attributed to proton quenching at the phenazine nitrogen atoms.

A molecular-level abacus-like system driven by light inputs has been designed in the form of a [2]rotaxane, comprising the pi-electron-donating macrocyclic polyether bis-p-phenylene-34-crown-10 (BPP34C10) and a dumbbell-shaped component that contains 1) a Ru(II) polypyridine complex as one of its stoppers in the form of a photoactive unit, 2) a p-terphenyl-type ring system as a rigid spacer, 3) a 4,4'-bipyridinium unit and a 3,3'-dimethyl-4,4'-bipyridinium unit as pi-electron-accepting stations, and 4) a tetraarylmethane group as the second stopper. The synthesis of the [2]rotaxane was accomplished in four successive stages. First of all, the dumbbell-shaped component of the [2]rotaxane was constructed by using conventional synthetic methodology to make 1) the so-called "west-side" comprised of the Ru(II) polypyridine complex linked by a bismethylene spacer to the p-terphenyl-type ring system terminated by a benzylic bromomethyl function and 2) the so-called "east-side" comprised of the tetraarylmethane group, attached by a polyether linkage to the bipyridinium unit, itself joined in turn by a trismethylene spacer to an incipient 3,3'-dimethyl-4,4'-bipyridinium unit. Next, 3) the "west-side" and "east-side" were fused together by means of an alkylation to give the dumbbell-shaped compound, which was 4) finally subjected to a thermodynamically driven slippage reaction, with BPP34C10 as the ring, to afford the [2]rotaxane. The structure of this interlocked molecular compound was characterized by mass spectrometry and NMR spectroscopy, which also established, along with cyclic voltammetry, the co-conformational behavior of the molecular shuttle. The stable translational isomer is the one in which the BPP34C10 component encircles the 4,4'-bipyridinium unit, in keeping with the fact that this station is a better pi-electron acceptor than the other station. This observation raises the question- can the BPP34C10 macrocycle be made to shuttle between the two stations by a sequence of photoinduced electron transfer processes? In order to find an answer to this question, the electrochemical, photophysical, and photochemical (under continuous and pulsed excitation) properties of the [2]rotaxane, its dumbbell-shaped component, and some model compounds containing electro- and photoactive units have been investigated. In an attempt to obtain the photoinduced abacus-like movement of the BPP34C10 macrocycle between the two stations, two strategies have been employed-one was based fully on processes that involved only the rotaxane components (intramolecular mechanism), while the other one required the help of external reactants (sacrificial mechanism). Both mechanisms imply a sequence of four steps (destabilization of the stable translational isomer, macrocyclic ring displacement, electronic reset, and nuclear reset) that have to compete with energy-wasteful steps. The results have demonstrated that photochemically driven switching can be performed successfully by the sacrificial mechanism, whereas, in the case of the intramolecu...

The photophysical properties of mono- and dinuclear complexes based on the bridging ligand tpphz (tpphz = tetrapyrido[3,2-a:2‘,3‘-c:3‘ ‘,2‘ ‘-h:2‘ ‘‘-3‘ ‘‘-j]phenazine) were investigated. The complexes are of general formula [M(bpy)2(tpphz)]2+ [M = Ru(II), Os(II)] and [(bpy)2M1(tpphz)M2(bpy)2] n + [M1= M2 = Ru(II), n = 4; M1= M2 = Os(II), n = 4; M1= Ru(II), M2 = Os(II), n = 4; M1= Ru(II), M2 = Os(III), n = 5]. The tpphz bridging ligand, being aromatic, rigid, and planar, has interesting structural features for the design of covalently linked donor−acceptor systems. In this work particular attention was devoted to the electronic properties of this bridge and their effect on the photophysical behavior. All of the results are consistent with direct involvement of the tpphz bridge in the photophysically active, lowest MLCT excited states. Relevant findings are as follows:  (i) in mononuclear complexes, MLCT excited-state energies are highly sensitive to interactions at the free bpy-like end of the tpphz ligand, such as metalation and protonation; (ii) in the dinuclear complexes, the electronic ground state behaves as a valence-localized, supramolecular system, while a substantial amount of intercomponent electronic coupling is indicated by MLCT excited-state behavior; (iii) in the heterodinuclear complex, fast (k > 109 s-1) energy and/or electron transfer processes take place across the tpphz bridge.

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