A new side-to-face supramolecular array of chromophores, where a pyridyl-substituted perylene bisimide dye axially binds to two ruthenium porphyrin fragments, has been prepared by self-assembly. The array is formulated as DPyPBI[Ru(TPP)(CO)](2), where DPyPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide and TPP = 5,10,15,20-tetraphenylporphyrin. The photophysical behavior of DPyPBI[Ru(TPP)(CO)](2) has been studied by fast (nanoseconds) and ultrafast (femtoseconds) time-resolved techniques. The observed behavior sharply changes with excitation wavelength, depending on whether the DPyPBI or Ru(TPP)(CO) units are excited. After DPyPBI excitation, the strong fluorescence typical of this unit is completely quenched, and time-resolved spectroscopy reveals the occurrence of photoinduced electron transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 5.6 ps) followed by charge recombination (tau = 270 ps). Upon excitation of the Ru(TPP)(CO) fragments, on the other hand, ultrafast (tau < 1 ps) intersystem crossing is followed by triplet energy transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 720 ps). The perylene-based triplet state decays to the ground state on a longer time scale (tau = 9.8 micros). The photophysics of this supramolecular array provides remarkable examples of (i) wavelength-dependent behavior (a small change in excitation wavelength causes a sharp switch from electron to energy transfer) and (ii) intramolecular sensitization (the triplet state of the perylene bisimide, inaccessible in the free dye, is efficiently populated in the array).

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Treatment of the octahedral Ru(II) complex [trans,cis,cis-RuCl(2)(DMSO-O)(2)(CO)(2)] with an equimolar amount of 5,10-bis(3'-pyridyl)-15,20-diphenylporphyrin (3'-cis-DPyP) yielded, upon selective replacement of the DMSO ligands, the neutral 2 + 2 metallacycle 2. NMR spectroscopy provided unambiguous evidence that only one highly symmetrical species, in which the two chromophores are held in a slipped cofacial arrangement by the external Ru(II) metal fragments, exists in solution. The unprecedented geometry of 2, and of the fully zincated analogue 2a, were confirmed in the solid state by X-ray structural investigations. The spatial arrangement of the two parallel chromophores in 2, with an interplanar distance of 4.18 A and a lateral offset (center-to-center distance) of 9.82 A, is reminiscent of those of the special pair of bacteriophylls in the reaction centers and of adjacent B850 units in the LH2 light-harvesting antenna systems of photosynthetic bacteria. For comparison, the X-ray structure of the corresponding metallacycle with 4'-cis-DPyP, 1a, is also reported. In 1a, the two porphyrins have an almost perfect coplanar arrangement. The semi-zincated metallacycles 1b and 2b, in which only one of the two chromophores bears an inner zinc atom, were prepared from 1 and 2, respectively, and isolated in pure form. Detailed photophysical investigations of the above porphyrin assemblies were performed. In particular, very fast photoinduced intercomponent energy transfer processes from the zinc porphyrin to the free-base unit were detected in the semi-metalated derivatives 1b and 2b (time constants: 14 and 12 ps, respectively).

Eight adducts between different pyridylporphyrins and ruthenium complexes, MPyP[RuCl(2)(DMSO)(2)(CO)], c-DPyP[RuCl(2)(DMSO)(2)(CO)](2), TrPyP[RuCl(2)(DMSO)(2)(CO)](3), TPyP[RuCl(2)(DMSO)(2)(CO)](4), (MPyP)(2)[RuCl(2)(DMSO)(2)], [c-DPyP[RuCl(2)(DMSO)(2)]](2), MPyP[RuCl(2)(CO)(3)], and [c-DPyP[RuCl(2)(CO)(2)]](2), have been investigated. The results show that in all the adducts the porphyrin singlet is quenched, to a greater or lesser extent, relative to the parent-free molecule. This study provides insight into the mechanisms of singlet quenching in the adducts. Two mechanisms for singlet quenching, both related to the "heavy-atom effect" of the ruthenium center and experimentally distinguishable by transient spectroscopy, are examined. Enhanced intersystem crossing within the porphyrin chromophore is demonstrated for the series of adducts MPyP[RuCl(2)(DMSO)(2)(CO)], c-DPyP[RuCl(2)(DMSO)(2)(CO)](2), TrPyP[RuCl(2)(DMSO)(2)(CO)](3), and TPyP[RuCl(2)(DMSO)(2)(CO)](4), where a nice correlation is observed between the magnitude of the effect and the number of ruthenium centers attached to the pyridylporphyrin chromophore. Singlet-triplet energy transfer from the pyridylporphyrin chromophore to the ruthenium center(s) is an additional efficient quenching channel for adducts containing ruthenium centers with weak field ligands and low triplet energies, such as (MPyP)(2)[RuCl(2)(DMSO)(2)] and [c-DPyP[RuCl(2)(DMSO)(2)]](2).

The supramolecular systems [Ru(Pyr(n)bpy)(CN)(4)](2-) (n = 1, 2), where one and two pyrenyl units are linked via two-methylene bridges to the [Ru(bpy)(CN)(4)](2-) chromophore, have been synthesized. The photophysical properties of these systems, which contain a highly solvatochromic metal complex moiety, have been investigated in water, methanol, and acetonitrile. In all solvents, prompt and efficient singlet-singlet energy transfer takes places from the pyrene to the inorganic moiety. Energy transfer at the triplet level, on the other hand, is dramatically solvent dependent. In water, the metal-to-ligand charge transfer (MLCT) emission of the Ru-based chromophore is completely quenched, and rapid (200 ps for n = 1) irreversible triplet energy transfer to the pyrene units is detected in ultrafast spectroscopy. In acetonitrile, the MLCT emission is practically unaffected by the presence of the pyrenyl chromophore, implying the absence of any intercomponent triplet energy transfer. In methanol, triplet energy transfer leads to an equilibrium between the excited chromophores, with considerable elongation of the MLCT lifetime. The investigation of the [Ru(Pyr(n)bpy)(CN)(4)](2-) systems in methanol provided a very detailed and self-consistent picture: (i) The initially formed MLCT state relaxes toward equilibrium in 0.5-1.3 ns (n = 1, 2), as monitored both by ultrafast transient absorption and by time-correlated single photon counting. (ii) The two excited chromophores decay with a common lifetime of 260-450 ns (n = 1, 2), as determined from the decay of MLCT emission (slow component) and of the pyrene triplet absorption. (iii) These equilibrium lifetimes are fully consistent with the excited-state partition of 12-6% MLCT (n = 1-2), independently measured from preexponential factors of the emission decay. Altogether, the results demonstrate how site-specific solvent effects can be used to control the direction of intercomponent energy flow in bichromophoric systems.

The investigated systems are side-to-face porphyrin arrays made of two types of molecular components: a porphyrin unit with meso-pyridyl substituents, and one or more ruthenium carbonyl tetraphenylporphyrin units. The two types of unit are assembled by axial coordination of the meso-pyridyl groups of the former onto the metal center of the latter. The number (one or four) of the meso-pyridyl groups on the axial unit determines whether the arrays are dimeric or pentameric. The geometry of the groups (4'-pyridyl or 3'-pyridyl) determine whether the arrays have perpendicular or canted structures. Furthermore, the meso-pyridyl porphyrin can be either free-base or zinc-substituted, leading to a total of eight different arrays. All arrays were shown to be stable in toluene, even in the dilute solutions (1x10 À5 m) required for photophysical experiments. The energy levels of the molecular components are practically unaltered in the arrays, with the excited states of the ruthenium porphyrin units always higher, both at the singlet and the triplet level, than those of the free-base or zinc porphyrin units. The photophysical behavior of the arrays has been studied in detail. The behavior was found to be practically independent of the perpendicular or canted nature of the systems. The arrays exhibit two main supramolecular features, distinctive with respect to the behavior of the monomeric molecular components (or suitable models thereof). At the singlet level, the behavior of the ruthenium unit is normal (100 % efficient intersystem crossing to the triplet state) but that of the axial unit is strongly perturbed, as indicated by pronounced fluorescence quenching. This effect is attributed to enhanced intersystem crossing in the free-base or zinc porphyrin unit, owing to the heavy-atom effect provided by the attached ruthenium units. At the triplet level, efficient energy transfer between the units takes place. When the axial unit is a free-base porphyrin, the driving force is large, and the process takes place irreversibly from the ruthenium to the free-base triplet. When the axial unit is a zinc porphyrin, the energy difference between the triplet states is small, and an equilibrium between the two states is established prior to deactivation. In the free-base systems, triplet energy transfer rate constants are found to be in the 10 8 ± 10 9 s À1 range.

The pentameric array of canted porphyrins (3‘TPyP)[Ru(TPP)(CO)]4 (1) (3‘TPyP = 5,10,15,20-tetra(3‘-pyridyl)porphyrin, TPP = meso-tetraphenylporphyrin) was synthesized by axial coordination of the 3‘N pyridyl groups of 3‘TPyP to the ruthenium core of four Ru(TPP)(CO) units; a thorough spectroscopic characterization of 1 in solution, together with a well-defined X-ray structure of the corresponding zinc derivative (Zn·3‘TPyP)[Ru(TPP)(CO)]4 (1Zn), is reported.

d] rate constants are found to be in the 10 8 ± 10 9 s À1 range.