New palladium and platinum metallacycles have been synthesized by reaction between a 2,7-diazapyrenium-based ligand and Pd(II) and Pt(II) complexes. The inclusion complexes between the metallacycles and polycyclic aromatic hydrocarbons (PAHs) in CD(3)NO(2) and D(2)O were studied by NMR spectroscopy. The structures of the inclusion complexes of the Pt metallacycle as host with pyrene, phenanthrene, and triphenylene were confirmed by single crystal X-ray crystallography. The association constants between the Pt metallacycle and the selected PAHs were determined in CH(3)CN following the characteristic charge-transfer band displayed in their UV/Vis absorption spectrum. Although in aqueous solution all the complexes showed a 1:1 stoichiometry, in CH(3)CN the Job plot indicated a 2:1 stoichiometry for complexes with triphenylene and benzo[a]pyrene. The estimated association constants in water correlate with the hydrophobicity of the PAH, indicating that hydrophobic forces play an important role in the complexation process.

A bidentate ligand based on N-monoaryl 4,4'-bipyridinium undergoes self-assembly to dinuclear rectangular metallocycles upon coordination to palladium(II) and platinum(II) centers. These metallocycles form a very stable complex with pyrene in aqueous solution and in the solid state. A crystal structure of the pyrene inclusion complex is presented. The association constants between pyrene and metallocycle 3a in organic solvents and water (K(a) = 2.3 x 10(6)) were determined.

Metrics & MoreArticle Recommendations CONSPECTUS: Stoddart's "blue box" (B 4+ ), is one of the most iconic molecules in the recent history of chemistry. This rectangular tetracationic cyclophane has not only the ability to complex a wide variety of aromatic guests in organic or aqueous media, but because of the presence of viologen units on its structure, it also behaves as a redox-based molecular switch. In turn, B 4+ -based host−guest complexes can translate this responsiveness from the molecular to the supramolecular level, resulting in host-controlled binding. This unique behavior has allowed the development of a wide variety of B 4+ -containing (supra)molecular switches and machines, which certainly have inspired a whole generation of supramolecular chemists. Nevertheless, issues, such as synthetic accessibility, structural diversity, or the implementation of new chemical properties (luminescence, pH-or photo-responsiveness, etc.), have restricted somehow the development of new practical applications in the ever-changing realm of modern host−guest chemistry. Based largely on our own research throughout the past decade, we will highlight in this account two different strategies for the selfassembly of new B 4+ analogues: (1) Pd(II)/Pt(II) metal-directed self-assembly and (2) hydrazone-based dynamic covalent chemistry. In essence, the strategies are based on the substitution of inert C−C single bonds on the macrocycle by Pd/Pt−N or C N bonds of modifiable lability. In the case of the metal-directed synthesis, the use of Pd(II) centers allows for the spontaneous selfassembly at r.t., either in organic or aqueous media, of N-alkyl-4,4′-bipyridinium-based ligands into the desired metallacycles.Conversely, more inert Pt(II) salts can be also implemented, rendering the synthesis of more kinetically stable analogues. Alternatively, wholly organic B 4+ congeners can be produced in a modular fashion by using hydrazone-based dynamic covalent chemistry, allowing for the self-assembly in acidic water of macrocyclic pH-responsive molecular switches of adjustable kinetic stability.Owning pyridinium-based cavities of appropriate size, our B 4+ -inspired cyclophanes are able to complex aromatic substrates by a conjunction of the hydrophobic effect and π−π/C−H•••π interactions. Consequently, we will discuss in detail the different host− guest complexes that can be achieved using our cyclophanes. Considering this knowledge, the implementation of our B 4+ -based macrocycles onto mechanically interlocked molecules and knots will be introduced, as well as the development of practical applications for the hosts in currently important research fields, such as the development of duplex and G4-DNA binders, supramolecular catalysis or the sequestration of relevant pollutants. Finally, self-assembled hosts offer the unique opportunity to include constitutional dynamism into host−guest chemistry, so examples of the development by our group of stimuli-responsive constitutionally dynamic libraries and self-sorted systems will be highligh...

The synthesis and the crystal structure of a doubly braided [2]catenane, a new molecular Solomon link, obtained by a 5-component-self-assembly process based on coordinative bonds, pi-donor/pi-acceptor interactions, and hydrogen bonding is reported.

Several new series of dendrimers containing a single redox-active 4,4'-bipyridinium (viologen) residue were synthesized and characterized. In these dendrimers, the viologen group is covalently attached to the apical position of a Newkome- or Frechet-type dendron, ranging in size from first to third generation of growth. The half-wave potentials corresponding to the two consecutive one-electron reductions of the viologen residue are affected by the size of the dendritic component. The size effects are more pronounced in the Newkome-type dendrimers and seem to result from the polarity contrast between the microenvironments provided by the solution and the internal phase of the dendrimer. Unlike in many other dendrimers having a redox-active core, the voltammetric behavior remains fast (reversible) even in third generation dendrimers. Pulse gradient stimulated echo NMR diffusion coefficient measurements on the Newkome-type dendrimers reveal that their hydrodynamic radii are relatively invariant in solvents of widely different polarities (dichloromethane to dimethyl sulfoxide). The host-guest binding interactions between the viologen residue in these dendrimers and the crown ether host bis-p-phenylene-34-crown-8 were also investigated. While in Newkome-type dendrimers the growth of the dendron caused a substantial attenuation of the binding constant values, this size effect was not observed in the Frechet-type dendrimers. These electrochemical and binding measurements underscore some of the structural differences between these two common types of dendritic architectures.

Concentration, temperature and/or solvent polarity control the speciation on the metal-directed self-assembly of a ditopic pyridyl ligand L with cis-protected Pd(ii) metal centers. This results into a controllable dynamic system, involving a [Pd2L2](6+) metallacycle and a [Pd4L4](12+) ring-in-ring complex.

New palladium and platinum metallocycles have been synthesized by reacting 4,4'-bipyridinium-based ligands with PdII and PtII complexes. Strict thermodynamic self-assembly of 1 and [M(en)(NO3)2] (M=Pd, Pt) 6 a,b afforded metallocycles 7 a,b. However, the synthesis of 8 a,b and 9 a,b required a self-assembly process that used sodium p-phenylenediacetate (12) as a template. Finally, metallocycles 10 a,b were synthesized under high dilution conditions from ligand 4. The formation of inclusion complexes between metallocycles 7-10 and substrates 13 and 14 were studied by low-temperature 1H NMR, and the association constants were determined in nitromethane and water by following the characteristic charge-transfer band that these metallomacrocycles show in their UV-visible absorption spectra. A clear correlation between the affinity for a substrate and the dimensions of the metallocycle was observed. Metallocycles 8 b and 9 b exhibited the highest binding constants in water and nitromethane. This observation is in agreement with the DFT (B3LYP)-optimized geometries obtained for the different metallomacrocycles, which indicate that only macrocycles 8 and 9 possess a cavity with a width larger than 3.5 A. The insertion of hydroquinone or diol 13 into the cavity of metallocycle 11 a was confirmed by single-crystal X-ray crystallography.

Dinuclear square metallocycles 3a,b assemble spontaneously when M(en)(OTf)2 (M = Pd, Pt) and a 4,4'-bipyridinium ligand are mixed in acetonitrile. Six new [3]catenanes were prepared in good yields by thermodynamically driven self-assembly reaction of molecular squares 3a,b and pi-complementary dioxoaryl cyclophanes. Single-crystal X-ray analyses of the [3]catenanes revealed the insertion of two aromatic units inside the metallocycle cavity. The structures are stabilized by means of a combination of pi-pi stacking, [C-H...pi] interactions, and [C-H...O] hydrogen bonds. [3]Catenane (DB24C8)2-(3a) showed in solid-state two external DB24C8 rings positioned over the Pd(en) corners, which are held in position by [N-H...O] hydrogen bonds. Furthermore, formation of catenane (DB24C8)2-(3a) can be switched off and on in a controllable manner by successive addition of KPF6 and 18-crown-6.