RESUMEN
New nitroxides based on aza-crown ethers were prepared and employed as selective sensors for the detection of inorganic and organic cations by EPR analysis of the corresponding host-guest complexes. The nitroxide unit behaves as a sensitive probe for a number of alkali and alkaline earth metal cations affording EPR spectra differing in the value of nitrogen hyperfine constants and in the appearance of splitted signals due to the non-zero nuclear spin of some metal cation upon complexation. Owing to the remarkable EPR spectral differences between the host and the corresponding cation complex the new macrocycles are likely to act as multitasking tools to recognize several cationic species. EPR behaviour of the larger nitroxide azacrown 1â when acting as a wheel in a radical synthetic bistable [2]rotaxane containing both secondary dialkylammonium and 1,2-bis(pyridinium) molecular stations, was also investigated. Reversible movements of the macrocycle between the two recognition sites in the rotaxane were promptly revealed by EPR, which shows significant changes either in nitrogen coupling constant values (aN ) or in the spectral shape in the two rotaxane co-conformations.
RESUMEN
Self-assembly with the square-planar Pd(II) or Pt(II) (en)M(ONO2)2 (en = ethylenediamine) complexes of ditopic ligands incorporating both N,N'-dialkyl-4,4'-bipyridinium and N-monoalkyl-4,4'-bipyridinium or N-monoalkyl-2,7-diazapyrenium moieties leads to constitutionally dynamic systems responsive to the concentration of the components. At low concentrations, the metallamacrocyclic mononuclear [ML]5+ species is formed. In contrast, when the concentration is increased, a defined dinuclear [M2L2]10+ structure appears as a second species in equilibrium, becoming the major one at high concentrations. Besides concentration changes, the addition of an aromatic guest also allows the control of the system speciation, shifting the outcome of the metal-directed self-assembly towards the mononuclear metallacycle. This dynamic behavior enables the control of the nuclearity of the metallacycles assembled by external stimuli.
RESUMEN
We present herein the "vermellogens", a new class of pH-responsive viologen analogues, which replace the direct linking between para-substituted pyridinium moieties within those by a hydrazone functional group. A series of such compounds have been efficiently synthesized in aqueous media by hydrazone exchange reactions, displaying a marked pH-responsivity. Furthermore, the parent N,N'-dimethylated "vermellogen": the "red thread", an analogue of the herbicide paraquat and used herein as a representative model of the series, showed anion-recognition abilities, non-reversible electrochemical behavior, and non-toxicity of the modified bis-pyridinium core. The host-guest chemistry for the "red thread" with the CB[7,8] macrocyclic receptors has been extensively studied experimentally and by dispersion corrected density functional theory methods, showing a parallel behavior to that previously described for the herbicide but, crucially, swapping the well-known redox reactive capabilities of the viologen-based inclusion complexes by acid-base supramolecular responsiveness.
Asunto(s)
Herbicidas , Viológenos , Paraquat/toxicidad , Aniones , Concentración de Iones de Hidrógeno , HidrazonasRESUMEN
The synthesis of new triphenylphosphonium-capped cucurbit[7]uril (CB[7])- and cucurbit[8]uril (CB[8])-based [2]rotaxanes was achieved by a simultaneous threading-capping strategy. While the use of CB[7] produced the designed [2]rotaxane, attempts to obtain the CB[8] analogue were unsuccessful due to the unexpected strong interaction found between the host and the phosphonium caps leading to pseudo-heteroternary host-guest complexes. This unusual binding motif has been extensively studied experimentally, with results in good agreement with those obtained by dispersion-corrected DFT methods.
Asunto(s)
Rotaxanos , Imidazoles/química , Rotaxanos/químicaRESUMEN
We present herein the development of a series of viologen-amino acid hybrids, obtained in good yields either by successive alkylations of 4,4'-bipyridine, or by Zincke reactions followed by a second alkylation step. The potential of the obtained amino acids has been exemplified, either as typical guests of the curcubituril family of hosts (particularly CB[7]/[8]) or as suitable building blocks for the solution/solid-phase synthesis of two model tripeptides with the viologen core inserted within their sequences.
Asunto(s)
Aminoácidos , Compuestos Macrocíclicos , Péptidos , ViológenosRESUMEN
Four bidentate, dicationic ligands (L12+-L42+) were prepared and investigated as guests for binding by the cucurbit[7]uril (CB[7]) host and structural components for metal (Pd and Pt)-coordinated self-assembly into metallacycles. In aqueous solutions, all the ligands were found to form stable complexes of variable stoichiometries with CB[7], and only one (L22+) failed to self-assemble, induced by the presence of suitable Pd or Pt complexes, into metallacycles. Exposure of the Pd-based metallacycles to CB[7] led to their disassembly at room temperature, while the Pt-based metallacycles remained stable under these conditions. However, heating of the Pt metallacycles in the presence of CB[7] also led to their disassembly. This interplay between the interactions in aqueous media of the L12+, L32+, and L42+ ligands with the CB[7] host and Pd (or Pt) complexes suggests the possibility of using these or related systems for controlled drug delivery applications.
Asunto(s)
Compuestos Macrocíclicos , Ligandos , AguaRESUMEN
Stoddart's "blue box" (B4+), 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, B4+-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 B4+-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 self-assembly of new B4+ 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 CâN bonds of modifiable lability. In the case of the metal-directed synthesis, the use of Pd(II) centers allows for the spontaneous self-assembly 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 B4+ 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 B4+-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 B4+-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 highlighted.
RESUMEN
Three molecular threads incorporating two viologen units attached by an oligo-ethylene glycol chain of variable length and an electron rich naphthalene moiety were prepared. The internal viologen unit is connected to the naphthalene by a rigid linker that prevents the simultaneous complexation of these systems. The axle with the shortest chain (14+) in the presence of CB[8] placed the chain inside the macrocycle in aqueous media. In contrast, the longer chains in 24+ and 34+ allow locating the terminal viologen and the electron rich unit inside the cavity. Upon reduction of the bipyridinium salts, the system behaves like a zip tie relaxing the chain as a consequence of the insertion of both radical cation moieties within the CB[8] and making these switches as potential components for molecular machinery.
RESUMEN
Synthetic supramolecular chemistry pursues not only the construction of new matter, but also control over its inherently dynamic behaviour. In this context, classic host-guest chemistry, based on the development of a myriad of macrocyclic receptors with fine-tuned affinities and selectivities, has enormously contributed to the discovery of new chemical function under self-assembly conditions. In turn, the use of molecular switches as control units within host-guest assemblies opened the door for the regulation of their dynamic interactional behaviour, which can be translated into controlled aggregation. In this review, we will focus on different strategies developed for the regulated binding of organic molecules by switchable macrocyclic hosts. As we will see, an appropriate design using stimuli-responsive versions of well-known organic receptors allows the molecular switches implemented within their structures to transform their regulated behaviour from the molecular to the supramolecular level.
RESUMEN
The self-assembly of [2]rotaxane has been achieved in aqueous media at pD 4 by the simultaneous threading into CB[7] of an appropriate axle ended with acyl hydrazine groups and its concurrent capping with two molecules of a triphenylphosphonium aldehyde as stoppers. The dynamism of the rotaxane has been demonstrated under acidic conditions and can be diminished by solvent swapping, pH modulation, or, surprisingly, the removal of the carbonyl groups on the axle.
RESUMEN
A series of aryl-extended N-monoalkyl-4,4'-bipyridinium salts L (aryl=1,4-phenyl, 4,4'-biphenyl, 2,6-naphthyl and 9,10-anthracenyl) have been implemented by PdII /PtII -directed self-assembly into constitutionally dynamic systems (CDSs). As a result, the intended processes produced not only (en)M2 L2 (en=ethylenediamine) metallacyclic species but also (en)M4 L4 ring-in-ring aggregates, in equilibrium with the former, as a consequence of the hydrophobic nature of the aryl rings within the 4,4'-bipyridinium scaffold. The key feature of the obtained dynamic systems is the possibility of modulating their response against external stimuli by modifying the hydrophobic character of the ligand. While the different dynamic libraries follow the same trends upon changes in concentration, temperature, polarity of the medium, or addition of an aromatic chemical effector, subtle changes in the ligand hydrophobic core results in a fine-tuning of the speciation when applying a certain degree of the different stimulus. The exception is the anthracene-containing derivative, which does not form inclusion complexes or self-threaded structures.
RESUMEN
A series of bis(pyridinium)-xylylene derivatives bearing carboxylate terminal groups were investigated as guests for the cucurbit[7]uril host in aqueous solution. While the presence of the terminal carboxylates has a modest effect on the thermodynamic stability of the complexes, the kinetics of complex association/dissociation is strongly affected. The relative position ( meta, para) of the carboxylate group in relation to the pyridinium nitrogen also exerts a considerable effect on the binding kinetics.
RESUMEN
We present herein the development of a new polycationic cyclophane: the "red box", second in a series of hydrazone-based analogues of the well-known organic receptor cyclobis(paraquat-p-phenylene)cyclophane ("blue box"). The macrocycle has been prepared in an excellent yield in aqueous media, and shows both a remarkable pH-responsiveness and unusual hydrolytic stability of the two hydrazone C[double bond, length as m-dash]N bonds, associated with charge delocalization of the amine lone pair. Whilst in aqueous media the "red box" is able to complex a variety of aromatic substrates, both in its acidic and basic form, in organic media the cyclophane is only able to capture those in the acidic form, resulting in supramolecular pH-responsiveness.
RESUMEN
We present herein the Pt(ii)-directed self-assembly in water of a new conformationally flexible N-monoalkyl-4,4-bipyridinium-based ditopic ligand into a library of six different metallacyclic structures. This constitutionally dynamic library can be pushed to increase the production of one of the supramolecules in aqueous media, either by controlling the concentration of the building blocks or upon addition of an appropriate aromatic substrate.
RESUMEN
We present here the design and synthesis of a series of multicomponent supramolecular architectures, structures formed by the PdII /PtII -directed integrative social self-sorting in aqueous media of pairs of complementary N-monoalkyl-4,4'-bipyridinium/2,7-diazapyrenium-based ligands. Out of the different potential outcomes of the processes, we have found out how the designed systems selectively enhance the production of pseudo[1]rotaxanes, hermaphroditic host-guest aggregates that maximize the strength of the occurring π-π, C-Hâ â â π, and hydrophobic interactions, as well as the number of those interactions per receptor. It is also demonstrated how both integrative social and narcissistic PdII -directed self-sorting can occur orthogonally and concomitantly for this type of ditopic ligands.
RESUMEN
We present here an efficient method for the preparation of non-symmetric viologen-containing ditopic ligands, as well as the Pd(ii)/Pt(ii)-directed self-assembly of some of these into metallacyclic receptors. The designed synthetic route, that implies the sequential alkylation and the Zincke reaction of activated bipyridinium salts, allowed us to substantially improve the yield in the preparation of three previously reported ligands. The versatility and efficiency of the method have also been tested for the preparation of four new viologen-containing ligands with very different structural features. Furthermore, the self-assembly of the new ligands around Pd(ii) and Pt(ii) centers has been tested, yielding mononuclear rectangular-shaped metallacycles of different dimensions and electronic characteristics.