Search

Oligophenylenevinylene (OPV)-terminated phenylenevinylene dendrons G1-G4 with one, two, four, and eight "side-arms", respectively, were prepared and attached to C60 by a 1,3-dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N-methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C60G1-C60G4, reaching a 99:1 ratio for C60G4 (antenna effect). UV/Vis and near-IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C60G1-C60G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free-energy change for electron transfer is the same along the series owing to the invariability of the donor-acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV-->C60 singlet energy transfer. In CH2Cl2, the OPV-->C60 electron transfer from the lowest fullerene singlet level ((1)C60*) is slightly exergonic (deltaG(CS) approximately = 0.07 eV), but is observed, to an increasing extent, only in the largest systems C60G2-C60G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV-->C60 electron transfer observed for C60G3 and C60G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer.

The synthesis and excited state properties of a compound assembling C60 with a new multi-photon absorption chromophore are reported.

The new, sterically encumbered phenanthroline ligands 1a,b, both characterized by the presence of bulky aryl substituents (3,5-di-tert-butyl-4-methoxyphenyl, 2,4,6-trimethylphenyl) in the 2,9-position, were prepared along with their homoleptic [Cu(1a,b)2]+ and heteroleptic complexes [Cu(1a,b)(phen)]+ (phen = parent 1,10-phenanthroline). Due to the pronounced steric shielding, particularly effective in ligand 1a, the formation of the homoleptic complex [Cu(1a)2]+ becomes very slow (5 days). Once formed, the homoleptic complexes [Cu(1a,b)2]+ do not exchange ligands even with phen added in excess because they are kinetically locked due to the large tert-butylphenyl substituents at the phenanthroline unit. The electronic absorption spectra of the homoleptic complexes [Cu(1a)2]+ and [Cu(1b)2]+ evidence a strongly different ground state geometry of the two compounds, the former being substantially more distorted. This trend is also observed in the excited-state geometry, as derived by emission spectra and lifetimes in CH2Cl2 solution. The less distorted [Cu(1b)2]+, compared to [Cu(1a)2]+, is characterized by a 15- and over 100-fold stronger emission at 298 and 77 K, respectively. Noticeably, the excited-state lifetime of [Cu(1a)2]+ in solution is unaffected by the presence of molecular oxygen and only slightly shortened in nucleophilic solvents. This unusual behavior supports the idea of a complex characterized by a "locked" coordination environment.

[structure: see text] Branched conjugated systems with a terminal alkyne function have been prepared starting from 4-(triisopropylsilylethynyl) phenylacetylene by applying the following iterative reaction sequence: (i) metal-catalyzed cross-coupling reaction of the terminal alkyne with 3,4-dibromobenzaldehyde or 2,5- dibromobenzaldehyde; (ii) Corey-Fuchs dibromoolefination and treatment with an excess of LDA. The building blocks thus prepared have been subjected to a Pd-catalyzed cross-coupling reaction with 1,4-diiodobenzene to yield isomeric branched pi-conjugated systems containing 7 (first generation) or 15 (second generation) phenyl units connected by ethynyl spacers. The different pi-conjugation patterns in those isomeric derivatives have a dramatic effect on their electronic properties, as attested by the differences observed in their absorption and emission spectra. Finally, theoretical calculations have been performed to rationalize the optical properties of these compounds.

Symmetrically substituted oligophenylenevinylene (OPV) derivatives bearing terminal p-nitrophenylhydrazone groups have been prepared and used for the synthesis of dumbbell-shaped bis(pyrazolino[60]fullerene)-OPV systems. In these triad arrays, the OPV-type fluorescence is dramatically quenched as a consequence of ultrafast OPV-->C60 singlet energy transfer. In its turn the fullerene singlet state is quenched by pyrazoline-->C60 electron transfer, in line with the behavior of the corresponding reference fullerene molecule. The occurrence of electron transfer in the multicomponent arrays is evidenced by recovery of fullerene fluorescence at 77 K in CH2Cl2 and in toluene at 298 K. Under these conditions the OPV-->C60 energy transfer is unaffected. The rate of this process turns out to be higher for the OPV trimer than for the corresponding pentameric OPV arrays, in agreement with energy-transfer theory expectations. Scanning tunneling microscopy (STM) and scanning force microscopy (SFM) revealed that the bis(pyrazolino[60]fullerene)-OPV can self-assemble into ordered layered crystalline architectures on the basal plane of highly oriented pyrolitic graphite.

The electrochemical and photophysical properties of molecular architectures consisting of oligomeric meso,meso-linked oligoporphyrin rods linked at both extremities to methanofullerene moieties are presented in comparison to those of model systems. Cyclic voltammetry data evidence the presence of a strong intramolecular electronic coupling along the porphyrin oligomers that varies slightly with their length. This interaction affects the redox potentials of both fullerene and porphyrin moieties. The electronic coupling between the two chromophores is confirmed by comparing the redox potentials of porphyrin arrays before and after attachment of the carbon sphere. Electronic absorption, fluorescence, and phosphorescence spectra of the porphyrin oligomers in toluene are reported, which provide the energy of the lowest singlet and triplet electronic excited states. In the fullerene-porphyrin conjugates, ground-state charge-transfer (CT) interactions are evidenced by low-energy absorption features above 750 nm. These systems also exhibit near-infrared (NIR) CT luminescence in toluene with lifetimes shorter than 1000 ps. On increasing the solvent polarity (from toluene to Et2O and THF), CT emissions become progressively weaker, red-shifted, and shorter lived, which reflects the energy-gap law and Marcus inverted region effects. Luminescence is not detected in benzonitrile. Picosecond transient absorption spectroscopy of the porphyrin-fullerene conjugates allows detection of the porphyrin cation as a clear fingerprint for electron transfer. The rate of charge recombination is in agreement with CT luminescence lifetimes, which confirms the occurrence of NIR radiative back-electron transfer.

The synthesis of a new ligand (1) containing a single phenanthroline (phen) chromophore and a flexibly connected diethylenetriamine tetracarboxylic acid unit (DTTA) as a lanthanide (Ln) coordination site is reported [1 is 4-[(9-methyl-1,10-phenantrol-2-yl)methyl]-1,4,7-triazaheptane-1,1,7,7-tetraacetic acid]. From 1, an extended series of water-soluble Ln.1 complexes was obtained, where Ln is Eu(III), Tb(III), Gd(III), Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III). The stoichiometry for the association was found 1:1, with an association constant K(A) > or = 10(7) s(-1) as determined by employing luminescence spectroscopy. The luminescence and photophysical properties of the series of lanthanide complexes were investigated in both H2O and D2O solutions. High efficiencies for the sensitized emission, phi(se), in air-equilibrated water were observed for the Ln.1 complexes of Eu(III) and Tb(III) in the visible region (phi(se) = 0.24 and 0.15, respectively) and of Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III) in the vis and/or near-infrared region [phi(se) = 2.5 x 10(-3), 5 x 10(-4), 3 x 10(-5), 2 x 10(-5), 2 x 10(-4), 4 x 10(-5), and (in D2O) 4 x 10(-5), respectively]. For Eu.1 and Tb.1, luminescence data for water and deuterated water allowed us to estimate that no solvent molecules (q) are bound to the ion centers (q = 0). Luminescence quenching by oxygen was investigated in selected cases.

Mononuclear complexes [Re(bpym)(CO)(3)Cl] and [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] (bpym = 2,2'-bipyrimidine), in which one of the bipyrimidine sites is vacant, have been used as "complex ligands" to prepare heterodinuclear d-f complexes in which a lanthanide tris(1,3-diketonate) unit is attached to the secondary bipyrimidine site to evaluate the ability of d-block chromophores to act as antennae for causing sensitized near-infrared (NIR) luminescence from adjacent lanthanide(III) centers. The two sets of complexes so prepared are [Re(CO)(3)Cl(mu-bpym)Ln(fod)(3)] (abbreviated as Re-Ln; where Ln = Yb, Nd, Er) and [(F(3)C-C(6)H(4)-CC)(2)Pt(mu-bpym)Ln(hfac)(3)] (abbreviated as Pt-Ln; where Ln = Nd, Gd). Members of both series have been structurally characterized; the metal-metal separation across the bipyrimidine bridge is approximately 6.3 A in each case. In these complexes, the (3)MLCT (MLCT = metal to ligand charge-transfer) luminescences of the mononuclear [Re(bpym)(CO)(3)Cl] and [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] complexes are quenched by energy transfer to those lanthanides (Ln = Yb, Nd, Er) that have low-lying f-f states capable of NIR luminescence; as a result, sensitized NIR luminescence is seen from the lanthanide center following excitation of the d-block unit. In the solid state, quenching of the luminescence from the d-block chromophore is complete, indicating efficient d --> f energy transfer, as a result of the short metal-metal separation across the bipyrimidine bridge. In a CH(2)Cl(2) solution, partial dissociation of the dinuclear complexes into the mononuclear units occurs, with the result that some (3)MLCT luminescence is observed from mononuclear [Re(bpym)(CO)(3)Cl] or [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] present in the equilibrium mixture. Solution UV-vis and luminescence titrations, carried out by the addition of portions of Ln(fod)(3)(H(2)O)(2) or Ln(hfac)(3)(H(2)O)(2) to the d-block complex ligands, indicate that binding of the lanthanide tris(1,3-diketonate) unit at the secondary bipyrimidine site to give the d-f dinuclear complexes occurs with an association constant of ca. 10(5) M(-)(1).

Highly soluble dendritic branches with fullerene subunits at the periphery and a carboxylic acid function at the focal point have been prepared by a convergent approach. They have been attached to an oligophenylenevinylene (OPV) core bearing two alcohol functions to yield dendrimers with two, four or eight peripheral C60 groups. Their photophysical properties have been systematically investigated in solvents of increasing polarity; that is, toluene, dichloromethane, and benzonitrile. Ultrafast OPV-->C60 singlet energy transfer takes place for the whole series of dendrimers, whatever the solvent. Electron transfer from the fullerene singlet is thermodynamically allowed in CH2Cl2 and benzonitrile, but not in apolar toluene. For a given solvent, the extent of electron transfer, signaled by the quenching of the fullerene fluorescence, is not the same along the series, despite the fact that identical electron transfer partners are present. By increasing the dendrimer size, electron transfer is progressively more difficult due to isolation of the central OPV core by the dendritic branches, which hampers solvent induced stabilization of charge separated couples. Compact structures of the hydrophobic dendrimers are favored in solvents of higher polarity. These structural effects are also able to rationalize the unexpected trends in singlet oxygen sensitization yields.

A multicomponent array made of a bis-copper(I) helicate core and two peripheral fullerene subunits has been prepared and electron transfer from the photoexcited Cu(I)-complexed unit to C60 occurs.

A new fullerene-substituted phenanthroline ligand has been obtained by reaction of a phenanthroline derivative bearing a 1,3-phenylenebis(methylene)-tethered bis-malonate with C(60) in a double Bingel cyclopropanation. The relative position of the two cyclopropane rings in the resulting bis-methanofullerene derivatives has been determined on the basis of the molecular symmetry (C(s)()) deduced from the (1)H and (13)C NMR spectra. The corresponding Cu(I) complex F-Cu-F has been prepared in good yields by treatment of the ligand with Cu(CH(3)CN)(4)BF(4). In the resulting multicomponent system, both C(60) moieties are in a tangential orientation relative to their bridging phenyl ring, and the central bis(phenanthroline)Cu(I) core is sandwiched between the two carbon spheres. The electrochemical properties of F-Cu-F suggest the existence of ground-state electronic interactions in this multicomponent array based on the mutual effects exerted by the fullerene units to the bis(2,9-diphenyl-1,10-phenanthroline)Cu(I) complex and vice versa. Close vicinity and electronic interactions between the inorganic core and the peripheral fullerene units are also suggested by increased electronic absorption around 430 nm. The distance between the two moieties is estimated to be 4.3 A by molecular modeling studies. The excited-state properties of F-Cu-F have also been investigated. Photoinduced electron transfer from the central chromophore to the external fullerene units occurs but, surprisingly, only following population of the excited states of the central inorganic unit and not of the external carbon spheres. This is mainly attributed to kinetic factors related to the different nature of the two types of excited states involved, namely charge transfer (excitation on the metal-complexed moiety) vs a localized state (excitation on the fullerene units).

Transient absorption spectrometry of Cu(I)-phenanthrolines in CH2Cl2 reveals ligand-independent dynamic processes lasting 15 ps, which are associated with the peculiar structural rearrangements occurring for this class of compounds upon photoexcitation.

After over 15 years of extensive research work in many laboratories worldwide, supramolecular photochemistry is a well-established and highly recognized branch of science. A brief retrospective view on the birth and infancy of this research area is given and some of the latest developments are discussed. In supramolecular photochemistry Ru(II) and Cu(I) diimmine complexes and C60 fullerenes are some of the most widely investigated chromophores and over the years big efforts have been made to implement and tune their photophysical and excited state properties, which are briefly reviewed. Thanks to a huge amount of synthetic and analytical research work, it has been possible to insert or combine these organic and inorganic subunits in a variety of fascinating supramolecular architectures. Some results concerned with photoinduced processes occurring in dyads, triads, catenanes, rotaxanes, dendrimers, and protonated self-assembled architectures are briefly illustrated. The overall picture stemming form the current state of the art in supramolecular photochemistry is that of a discipline gaining an increasing degree of multidisciplinarity. Interconnections with biology, physics and information technology are being established at a very fast pace, suggesting a bright future for this still young research field.

Owing to their special photophysical properties, fullerene derivatives are good candidates to demonstrate dendritic effects. In particular, the triplet lifetimes of a C(60) core can be used to evaluate its degree of isolation from external contacts. On the other hand, the fullerene core can act as a terminal energy receptor in dendrimer-based light-harvesting systems. When a fullerodendrimer is further functionalized with a suitable electron donor, it may exhibit the essential features of a multicomponent artificial photosynthetic system in which photoinduced energy transfer from the antenna to the C(60) core is followed by electron transfer.

Steady-state and time-resolved spectroscopic properties of bichromophoric species containing [Ru(bpy)(3)](2+) and pyrene (pyr) units linked together by flexible poly(ethylene glycol) chains of variable length, [Ru(bpy)(2)(bpy-pyr)](PF(6))(2) (1) and [Ru(bpy)(2)(bpy-O6-pyr)](PF(6))(2) (2), have been investigated in acetonitrile solvent. The complexes were designed with the aim of examining the intercomponent energy-transfer processes taking place after light absorption at the two chromophores and the influence of the distance separation between them; in the case of complex 2, the linking chain in the extended conformation is as long as 21 A. Direct excitation of the pyrene unit (lambda(exc) = 410 nm) results in singlet-to-singlet energy transfer (an antenna effect) to the Ru-based component, (1)pyr --> (1)MLCT, which we analyze in terms of the Förster mechanism taking place with unit efficiency. Analysis of the time-resolved pyrene fluorescence reveals that the actual center-to-center distance separation (d(cc)) between the photoactive centers changes according to a Gaussian distribution, with an average d(cc) = 13.6 A (distribution width, a = 2.8 A) and 12 A (a = 10.2 A), for 1 and 2, respectively; this is ascribed to folding of the poly(ethylene glycol) linking chain. In O(2)-free solvent at room temperature, after population of the (1)MLCT level (which takes place either because of direct excitation by using lambda(exc) > 355 nm or via the "antenna" effect) and subsequent intersystem crossing localized at the Ru center, (1)MLCT --> (3)MLCT, a triplet-triplet thermal equilibration is established which involves the physically separated centers, (3)MLCT <--> (3)pyr, with K(eq) = 11 (the energy gap between the two levels is 480 cm(-1), as determined from luminescence data obtained at 77 K). As a consequence of this equilibrium, the (3)MLCT luminescence lifetime becomes tau(Ru) approximately 9 micros both in 1 and 2, i.e., 1 order of magnitude longer than for the unsubstituted [Ru(bpy)(3)](2+) luminophore. In air-equilibrated solvent, diffusional quenching by O(2) effectively depletes the (3)pyr level and only the forward (3)MLCT --> (3)pyr energy transfer step is observed with k(en) = 4 x 10(8) and 2 x 10(8) s(-1) for 1 and 2, respectively. As briefly discussed, reasons for the high rate constants observed for the various triplet-triplet steps may be traced back to the folding properties of the linking chains.

Dendrimers with an electroactive bis(phenanthroline) copper(I) core have been prepared and thin layer cyclic voltammetry (TLCV) found to be an efficient tool to determine their redox characteristics in spite of the slow electron transfer kinetics observed for the largest compounds.

A two-component ligand system (1) containing 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) as the hosting unit for the lanthanide cations and an appended asymmetrically functionalized 1,10-phenanthroline (phen) as the chromophore was synthesized. The 1:1 complexes with Eu(3+), Gd(3+), Tb(3+), and Yb(3+) have been prepared and studied in aqueous solution. For Gd.1, a relaxivity value of 2.4 mM(-1) s(-1) has been measured at 20 MHz and 25 degrees C, which indicates that there are no water molecules in the first coordination sphere of the metal ion. The analysis of high resolution (1)H NMR spectra of Yb.1 supports this view and suggests the direct involvement of the phen moiety in the coordination of the metal ion. For Eu.1 and Tb.1, the absorption and luminescence spectra, the overall luminescence efficiencies, and the metal-centered (MC) lifetimes were obtained; coordination features were also determined by comparing luminescence properties in water and deuterated water. For Eu.1 and Tb.1, the overall emission sensitization (se) process in air-equilibrated water was found to be notably effective with phi(se) = 0.21 and 0.11, respectively. A detailed study of the steps originating from light absorption at the phen unit and leading to MC sensitized emission was performed.

The rhenium(I) and ruthenium(II) complexes of a fullerene-substituted bipyridine ligand have been prepared. Electrochemical studies indicate that some ground state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in the Re(I) but not the Ru(II) complex. The photophysical properties have been investigated by steady-state and time-resolved UV/Vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in CH2Cl2 solution, and compared to those of the corresponding model compounds. Excitation of the methanofullerene moiety in the dyads does not lead to excited state intercomponent interactions. Instead, excitation of the metal-complexed unit shows that the lowest triplet metal-to-ligand-charge-transfer excited state ((3)MLCT) centered on the Re(I)- or Ru(II)-type unit is quenched with a rate constant of about 2.5 x 10(8) s(-1). The quenching is attributed to an electron-transfer (ElT) process leading to the reduction of the carbon sphere, as determined by luminescence spectroscopy for the Ru(II) dyad. Experimental detection of electron transfer in the Re(I) dyad is prevented due to the unfavorable absorption of the metal-complexed moiety relative to the fullerene unit. However, it can be postulated on the basis of energetic/kinetic arguments and by comparison with the Ru(II)-type array. The primary ElT process is followed by charge-recombination to give the lowest-lying fullerene triplet excited state (3C60) with quantitative yield, as determined by sensitized singlet oxygen luminescence experiments. Direct (3)MLCT-->3C60 triplet-triplet energy-transfer (EnT) does not successfully compete with ElT since it is highly exoergonic and located in the Marcus inverted region. The quantum yield of singlet oxygen sensitization (Phi(delta)) of the Re(I)-based dyad is found to be lower (0.80) than for the corresponding Ru(II) derivative (1.0). This is likely to be the consequence of different conformational structures for the two dyads, rather than a different yield of 3C60 formation.

Assemblies of four oligophenylenevinylene moieties arising from a calix[4]arene core, i.e., calix[4]oligophenylenevinylenes, have been prepared by Heck-type cross-coupling reactions of styrene derivatives with a tetraiodinated cone-calix[4]arene precursor. Photophysical studies in solution have revealed that there are electronic ground state interactions between the covalently bonded OPV moieties. The absorption spectra of the calix[4]oligophenylenevinylenes are significantly different from those obtained by summing the spectra of four model units and their emission is red-shifted when compared to the corresponding model compounds. Electrochemical studies have shown that the redox processes of the four OPV subunits do not take place at the same potentials indicating also a strong electronic interaction among them in the calix[4]oligophenylenevinylenes.

We synthesized new [Cu(NN)(2)](+)-type complexes where NN = 2-5 and denotes a 2,9-disubstituted-1,10-phenanthroline ligand (related complexes of 1 and 6 ligands are used for reference purposes). For 2, 3, and 4 the ligand substituents are long alkyl-type fragments, whereas in 5 a phenyl ring is directly attached to the chelating unit. At 298 K the four complexes display relatively intense metal-to-ligand-charge-transfer (MLCT) emission bands with maxima around 720 nm, Phi(em) approximately 1 x 10(-)(3) and tau > 100 ns in deaerated CH(2)Cl(2). The emission behavior at 77 K in a CH(2)Cl(2)/MeOH matrix is quite different for complexes of alkyl- (2-4) versus phenyl-substituted (5) ligands. The former exhibit very intense emission bands centered around 642 nm and hypsochromically shifted with respect to 298 K, whereas the luminescence band of [Cu(5)(2)](+) is faint and shifted toward the infrared side. These results prompted us to study in detail the temperature dependence of luminescence properties of [Cu(2)(2)](+) and [Cu(5)(2)](+) in the 300-96 K range. For both complexes the excited state lifetimes increase monotonically by decreasing temperatures, and the trend is well described by an Arrhenius-type treatment involving two equilibrated MLCT excited levels. The emission bands show a similar behavior for the two compounds (intensity decrease and red-shift) only in the 300-120 K range, when the solvent is fluid. In the frozen regime (T

The cyclophane-type molecular dyads 1 x 2H and 1 x Zn, in which a doubly bridged porphyrin donor adopts a close, tangential orientation relative to the surface of a fullerene acceptor, were prepared by Bingel macrocylization. The porphyrin derivatives 2 x 2H and 2 x Zn with two appended, singly linked C60 moieties were also formed as side products. NMR investigations revealed that the latter compounds strongly prefer conformations with one of the carbon spheres nesting on the porphyrin surface, thereby taking a similar orientation to that of the fullerene moiety in the doubly bridged systems. Cyclic voltammetric measurements showed that the mutual electronic effects exerted by the fullerene on the porphyrin and vice versa are only small in all four dyads, despite the close proximity of the donor and acceptor components. The steady-state and time-resolved absorption and luminescence properties of 1 x Zn and 2 x Zn were investigated in toluene solution and it was shown that, upon light excitation, both the porphyrin- and the fullerene-centered excited states are deactivated to a lower-lying CT state, emitting in the IR spectral region (lambda max = 890 and 800 nm at 298 and 77 K, respectively). In the more polar solvent benzonitrile, this CT state is still detected but, owing to its very low energy (below 1.4 eV), is not luminescent and shorter-lived than in toluene. The remarkable observation of similar photophysical behavior of 1 x Zn and 2 x Zn suggests that a tight donor-acceptor distance cannot only be established in doubly bridged cyclophane-type structures but also in singly bridged dyads, by taking advantage of favourable fullerene-porphyrin ground-state interactions.

Virtual inaccessibility to external contact was revealed by electrochemical investigations for a bis(1,10-phenanthroline)copper(I) core embedded in dendrimers with up to 16 peripheral fullerene units (shown schematically). With increasing numbers of fullerene units, less and less light is available to the core, and the small quantity of light energy that reaches the central Cu(I) complex is returned to the external fullerenes by energy transfer-the central core is buried in a dendritic black box.

By applying the three-dimensional template effect of copper(I), previously used for making various interlocking ring systems, a new disymmetrical [2]-catenate has been made which consists of two different interlocking rings. One ring contains a 2,9-diphenyl-1,10-phenanthroline (dpp) unit whereas the other cycle incorporates both a dpp motif and a 2,2',6',2''-terpyridine (terpy) fragment, the coordination site of these two chelates pointing toward the inside of the ring. Depending on the oxidation state of the central metal (Cu(I) or Cu(II)), and thus on its preferred coordination number, two distinct situations have been observed. With monovalent copper, the two dpp units interact with the metal and the terpy fragment remains free, at the outside of the molecule. By contrast, when the catenate is complexed to divalent copper, the terpy motif is bonded to the metal and it is now a dpp ligand which lies at the periphery of the complex. This dual coordination mode leads to dramatically different molecular shapes and properties for both forms. The molecular motion which interconverts the four- and the five-coordinate complexes can be triggered chemically, electrochemically, or photochemically by changing the oxidation state of the copper center (II/I). The process has been studied by electrochemistry and by UV-vis spectroscopy. Interestingly, once the stable 4-coordinate copper(I) complex has been oxidized to a thermodynamically unstable pseudo-tetrahedral copper(II) species, the rate of the gliding motion of the rings which will afford the stable 5-coordinate species (copper(II) coordinated to dpp and terpy) can be controlled at will. Under certain experimental conditions, the changeover process is extremely slow (weeks), and the 4-coordinate complex is more or less frozen. By contrast, addition of a coordinating counterion to the medium (Cl - ) enormously speeds up the rearrangement and leads to the thermodynamically stable 5-coordinate complex within minutes.