The influence of metal-complexing macrocycle size on intramolecular movement in rotaxanes.

[2]rotaxanes composed of a dibenzo-24-crown-8 wheel (DB24C8) and an axle containing two metal-complexing tetraazamacrocyclic units linked with a p-xylylene bridge, coordinating the same or different metal ions (Ni and/or Cu) are described. A symmetric di-Ni rotaxane crystallizes in the monoclinic P21/c space group with one rotaxane cation and four PF6- counterions in the asymmetric part of the unit cell. In the crystal, the cations and anions of the investigated compound form an intertwined 3D-framework with C-HF and C-Hπ intermolecular interactions. The NMR ROESY spectrum of the diamagnetic di-Ni rotaxane confirms that at room temperature slow shuttling of the DB24C8 moiety takes place along the symmetric axle. The non-symmetric rotaxane, containing 14- and 16-membered nickel(ii)-complexing macrocycles, exists in solution as an equilibrium mixture of two conformers in the ratio of ca. 1 : 7. This rotaxane behaves as a potential-controlled molecular switch: in the major isomer, the DB24C8 moiety is localized in the vicinity of the 14-membered metal-complexing macrocycle, and moves towards the 16-membered unit upon the first oxidation. Reverse translocation occurs after the subsequent oxidation of the 14-membered complex unit. In contrast, no such movements of the DB24C8 moiety were observed upon investigation of the heteronuclear [2]rotaxane, coordinating copper(ii) and nickel(ii) ions.

Neutral bis-macrocyclic nickel(II) and copper(II) complexes as π-donor receptors.

A new type of hetero- and homo-polynuclear complexes of copper(II) and nickel(II) containing 1,2,3-triazole groups in polymethylene chains have been synthesized and characterized using NMR and electrochemical methods. The triazole link facilitates the synthesis of hetero-dinuclear macrocyclic complexes. Introducing the triazole unit into the complex structure can lead to increased stability of the bis-macrocyclic system and to obtain electroactive receptors for electron-deficient molecules. Intermolecular interactions between new bis-macrocyclic donors and a chosen acceptor--7,7,8,8-tetracyanoquinodimethane (TCNQ) have been studied by voltammetry. Normal pulse voltammetry with varying initial potentials, E(i), was found to be a convenient tool to follow subtle changes of the electrochemical behavior of the redox centers due to interactions between the π-donor, bis-macrocyclic complex, and the acceptor, TCNQ molecule. The copper(II) bis-macrocyclic compound functions as a receptor able to accommodate the small organic compound in the macrocyclic cavity. This brings together transition metal ions and organic substrates within the same supramolecular structure.

Pseudorotaxane based on tetraazamacrocyclic copper complex and dibenzocrown ether.

Host-guest interactions between two electron-rich dibenzocrown ethers and electron deficient macrocyclic copper(II) tetraimine complexes lead to the formation of pseudorotaxane in solution. The interactions are enhanced with the copper(III) complex compared to that of the copper(II) form as shown by the electrochemical studies. The larger--30-membered dibenzocrown donor interacted with the copper complex stronger than the smaller ones as revealed by NMR and electrochemical methods. The thiolated form of the copper(II) tetraimine complex was self-assembled at the gold electrode forming an electroactive monolayer able to interact with the crown ether in the solution. These donor-acceptor interactions lead to an increase of the barrier properties of the layer and decreased the electron transfer rate between the copper centre and the gold electrode surface as proved by the voltammetric data.

Macrocyclic multicenter complexes of nickel and copper of increasing complexity.

Multicenter (bi-, tri-, and tetranuclear) tetraazamacrocyclic complexes were self-assembled from Ni and Cu tetraazamacrocyclic mononuclear units and α,ω-diamines as building blocks. The structures of all compounds studied were proved by spectroscopic methods (ESI MS and NMR spectroscopy). Electrochemical experiments revealed reversible one-electron electrode processes at each of the Ni(2+) and Cu(2+) centers with formation of metal cations in oxidation state +3. Long linkers allow bi- and trinuclear complexes with noninteracting metal centers to be obtained. In the case of the short linkers (e.g. ethylenediamine) higher, trinuclear species are formed as major product. The structures of the bis- and tris-macrocyclic systems were confirmed by single-crystal X-ray diffraction. The tris-macrocyclic systems form cations in the shape of triangles partially filled with counterions and solvent molecules. The cations form positively charged layers, which interact in the crystal lattice with the neighboring negatively charged layers of anions. In solution, the trinuclear complexes exhibit strong host-guest interactions with 9,10-dimethyltriptycene due to complementarity of shape and size of this guest molecule. The association constants were determined by NMR spectroscopy and voltammetry, and very good agreement was obtained. The structural flexibility of the tetranuclear complex with long linkers allows for attractive interactions between the metal-complexing macrocycles that result in folding of the molecule. On the contrary, no folding is possible in the case of short linkers consisting of two CH(2) groups.

Face-to-face dinuclear scaffolds composed of tetraazamacrocyclic charged and neutral complexes.

A new family of bismacrocyclic homo- and heteronuclear Ni and Cu complexes has been synthesized and characterized. The ligand scaffold is comprised of two 14-membered tetraazamacrocyclic sites held in cofacial orientation. The dinuclear complexes are unique in that one macrocyclic center is neutral while the other one is charged, although the ligand backbones are nearly identical. This leads to a binuclear system of two structurally similar components, differing in their electron-donor abilities. The crystallographically characterized structures in the solid state revealed similarity of the four dinuclear complexes studied. The metal-metal separations are between 4 and 5 A. The strongest electrostatic intramolecular interactions occur in the molecules with neutral and charged components, most differing in donor abilities.

Interactions of dithiolated tetraazamacrocyclic copper(II) and nickel(II) complexes self-assembled on gold electrodes with pi-electron deficient molecules in solution.

Self-assembled monolayers of dithiolated neutral monotetraazamacrocyclic complexes of copper(II) and nickel(II) can provide molecularly defined platforms for the formation of a pseudorotaxane-like nanostructures on the gold electrode surface. We propose these complexes as pi-donor building blocks for the construction of new molecular devices. We show that these perpendicularly oriented macrocyclic complexes anchored to the electrode surface act as pi-electron rich species interacting with pi-electron deficient compounds dissolved in solution, such as fluorine derivatives of tetracyanoquinodimethane (F(4)TCNQ) or a charged bismacrocyclic tetraaza complex of copper(II). The interactions of the surface immobilized macrocyclic complexes with F(4)TCNQ and with ring-shaped acceptor molecules are monitored and characterized by linear scan voltammetry. The interactions with the bismacrocyclic compound lead to a new pseudorotaxane array supported on the electrode surface and switched on and off by the application of appropriate potentials.

Determination of experimental charge density in model nickel macrocycle: [3,11-bis(methoxycarbonyl)-1,5,9,13-tetraazacyclohexadeca-1,3,9,11-tetraenato-(2-)-kappa(4)N]nickel(II).

Experimental and theoretical atomic charges and d-orbital populations were obtained for [3,11-bis(methoxycarbonyl)-1,5,9,13-tetraazacyclohexadeca-1,3,9,11-tetraenato(2-)-kappa(4)N]nickel(II) monocrystal (16Ni) using the Hansen and Coppens formalism. Several models of this structure were tested as a function of quality of the fit, convergence of the refinement, value of residual peaks and holes, and Hirshfeld's rigid-bond test. The models with Ni-atomic scattering factors applied for the metal center are significantly better than those with the Ni-ionic scattering factors. The properties of the final electron density distributions are very consistent and similar for all of the models tested. The values of the d-orbital populations for Ni roughly agree with the occupation order of the d-electron levels for square-planar complexes derived from crystal field theory and are comparable with those obtained by the natural population analysis method. Experimental atoms-in-molecules charges calculated for four different models agree quite well for models with different symmetry restrictions and the same scattering factor for the Ni. Both experimental and theoretical methods predict relatively high negative values of charges for the nitrogen and oxygen atoms and also a quite high positive charge for the C(7) atom. The values of rho(r(BCP)) for the Ni-N bonds are in the range from 0.60 up to 0.75e A(-3), with positive laplacian values indicating noncovalent bonding. For the laplacian of the electron density evaluated in the plane of the macrocyclic ring, a typical map for a square-planar complex was obtained with four charge concentrations--3d(xy) orbitals--pointing toward the regions between the M-N bonds and charge depletions directed toward the (3,-1) critical points of the negative laplacian for the nitrogen atoms.

Neutral nickel(II) and copper(II) tetraazamacrocyclic complexes as molecular rods attached to gold electrodes.

New dithiolated derivatives of neutral Cu(II) and Ni(II) tetraazamacrocyclic complexes have been synthesized and characterized by spectroscopic and diffractional methods. These rod-shaped molecules were assembled in monocomponent and mixed monolayers on gold electrodes. In the mixed monolayers, the active molecules were embedded in a hexanethiol matrix. The dithiolated complexes are oriented perpendicularly to the electrode, and reveal faster kinetics of electron transfer than those assembled in a single-component monolayer. They appear as protrusions, which are easily addressed by using the STM method. In the presence of a suitable electron acceptor in the solution, the donor properties of the anchored Cu complex were weakened, which revealed donor-acceptor interactions with the monolayer. The peak position in the voltammogram indicates a stronger interaction of the solution-based acceptor with the reduced Cu(II) form than with the Cu(III) complex. This suggests the possibility of switching the association on or off by applying an appropriate potential.

Fine-tuning of properties of bismacrocyclic dinuclear cyclidene receptors by N-methylation.

N-Methylated bismacrocyclic Cu and Ni complexes were synthesised and structurally characterised in the solid state. Their properties in solution were analysed by using NMR and ESR spectroscopies and electrochemical methods. Face-to-face biscyclidenes linked through polymethylene chains form rectangular boxlike cations. These moieties can host some small guest molecules (water, pi-electron donating compounds) and are stabilised by a shell of neighbouring counterions. For the bismacrocyclic dinuclear complexes containing two nickel or two copper ions, the intramolecular interactions between the metallic centres are strengthened through methylation of the macrocyclic components, as compared with the nonmethylated species. We report the electron coupling created by two unpaired electrons coming from two copper centres observed by ESR spectroscopy. Methylation weakens the electron-acceptor properties of the complexes, which leads to less effective binding of the pi-electron-donating guests. It also increases the stability of the lower oxidation states. In the case of the copper complexes, both Cu(II)/Cu(I) and Cu(II)/Cu(III) reversible one-electron transfers are seen in the voltammograms. These changes in properties are interpreted as the consequences of steric repulsion between the methyl substituents and the macrocyclic ring.

Intermetallic interactions in face-to-face homo- and heterodinuclear bismacrocyclic complexes of copper(II) and nickel(II).

New face-to-face heterodinuclear complexes containing copper(II) and nickel(II) in identical tetraazamacrocyclic environments have been synthesized and characterized using ESI mass-spectrometry, X-ray diffraction, spectroscopic methods, and elemental analysis. These new bismacrocyclic systems were compared with the respective mono- and bismacrocyclic and [2]catenane homonuclear complexes. Interactions between the metal centers were monitored by magnetic and electrochemical measurements. Magnetic data indicate that all copper compounds studied behave as weakly interacting magnets. In the case of copper [2]catenane, the extent of magnetic interactions decreased when a benzocrown moiety was introduced between the macrocyclic units. On the basis of electrochemical data, the interactions between the metal centers were found to be substantially larger for the nickel complexes than for the corresponding copper ones. Interlocking of a benzocrown ether to form [2]catenane led to a nonequivalence of the metal centers and to the increase of donor abilities of the catenane compared to the respective bismacrocyclic complex. This is reflected by the shift of the first formal potential to less positive values. Intermetallic interactions for the heteronuclear nickel/copper complexes were found intermediary compared to the homonuclear ones. They were strengthened by shortening the spacer between the two tetraazamacrocyclic subunits which is a convenient way of fine-tuning the interactions. The increase of intermetallic interactions led to the increased stability of the intermediate mixed-valence states indicated by the higher values of comproportionation constants.