Luminescent Ln-Pt2 metallohairpin complexes have been developed, and their intercalative recognition with DNA has been demonstrated with linear dichroism spectroscopy. The heterotrimetallic complexes were formed in a one-step reaction, by assembly of an aminopolycarboxylate ligand, a platinum terpyridine unit, and the lanthanide salt. The metallohairpin complexes bear a neutral lanthanide moiety and two positively charged platinum-containing intercalating units. The Nd(III) analogues are luminescent in the near infrared, and this near-IR luminescence is retained upon binding to DNA. The DNA recognition was demonstrated by linear dichroism spectroscopy. The linear dichroism spectra suggested that the complexes bind perpendicular to the DNA helical axis, confirming intercalative recognition accompanied by dramatic stiffening of DNA, which suggests bis-intercalation of the complex.
Multiple competing molecular interactions (metal–ligand, π‐stacking and hydrogen‐bonding) in the silver(I) complexes of 4′‐thiomethyl‐2,2′:6′,2″‐terpyridine give rise to a range of different molecular architectures, in which the metal–ligand coordination requirements are satisfied in quite different ways. Polynuclear supramolecular spirals, aggregated mononuclear and aggregated dinuclear units are all structurally characterised. The metallo‐supramolecular architecture obtained displays a remarkable dependence both on the choice of non‐coordinated anion and the type of solvent used (coordinating or non‐coordinating). The anion dependence is particularly surprising, since the anions are not integrated into the centre of the supramolecular structure. The solution behaviour is also solvent and anion dependent, with aggregation of planar mononuclear cations observed in acetonitrile, but oligonuclear spiral species implicated in nitromethane. The extraordinarily variable geometries of these systems suggest that they provide a novel example of the “frustration” principle, in which opposing tendencies cannot simultaneously be satisfied and identify an alternative approach to the design of metallo‐supramolecular systems whose structure is responsive to external agents.
The effect of inter-strand and intra-strand interactions is explored in a metallo-supramolecular system in which the metal-ligand coordination requirements may be satisfied by more than one different supramolecular architecture. This is achieved by introducing alkyl substituents onto the spacers of readily prepared bis(pyridylimine) ligands. The alkyl substituents induce twisting within the ligand strand and this intra-strand effect favours formation of helical architectures. The alkyl substituents also introduce inter-strand CH.pi interactions into the system. For the smaller methyl group these are most effectively accommodated in a trinuclear circular helicate architecture. A solution mixture of dinuclear double-helicate and trinuclear circular helicate results from which, for copper(I), the trinuclear circular helicate crystallises. The CH.pi interactions endow the circular helicate with a bowl-shaped conformation and the triangular unit aggregates into a tetrahedral ball-shaped array. Low-temperature NMR studies indicate that the CH.pi interactions also confer a bowl-shaped conformation on the triangle in solution. The larger ethyl groups can sustain intra-strand CH.pi interactions in the lower nuclearity double-helical system and this is the unique architecture for that ligand system in both solution and the solid state. Crystal structures are described for both the copper(I) and silver(I) complexes. Thus we show that intra-strand interactions may be used to induce helicity within this system, while the nuclearity of the array can be prescribed by the inter-strand interactions.
The enantiomeric resolution of an extended range of di-metallo supramolecular triple-helical molecules are reported. The ligands for all complexes are symmetric with two units containing an aryl group linked via an imine bond to a pyridine. Alkyl substituents have been attached in different positions on the ligand backbone. Previous work on the parent compound, whose molecular formula is [Fe(2)(C(25)H(20)N(4))(3)]Cl4, showed that it could be resolved into enantiomerically pure solutions using cellulose and 20 mM aqueous sodium chloride. In this work a range of mobile phases have been investigated to see if the separation and speed of elution could be increased and the amount of NaCl co-eluted with the compounds decreased. Methanol, ethanol and acetonitrile were considered, together with aqueous NaCl : organic mixtures. Effective separation was most often achieved when using 90% acetonitrile : 10% 20 mM NaCl (aq) w/v, which gives scope for scaling up to incorporate the use of HPLC. The overall most efficient (i.e. fastest) separation was generally achieved where the cellulose column was packed with 20 mM NaCl (aq) and the column first eluted with 100% acetonitrile, then with 75% ethanol : 25% 20 mM NaCl (aq) until the M enantiomer had fully eluted and finally with 90% acetonitrile : 10% 20 mM NaCl (aq) until the P enantiomer had been collected. The sequence of eluents ensured minimum NaCl accompanying the enantiomers and minimum total solvent being required to elute the enantiomers, especially the second one, from the column. No helicate with a methyl group on the imine bond could be resolved and methyl groups on the pyridine rings also have an adverse effect on resolution.
The DNA binding of a dicationic pyridylimine-based dicopper(I) metallosupramolecular cylinder is reported together with its ability to act as an artificial nuclease. The cylinder binds strongly to DNA; more strongly than the spherical dication [Ru(phen)(3)](2+) (phen=1,10-phenanthroline), but more weakly than the corresponding tetracationic cylinders. DNA coiling effects are not observed with this dication, in contrast to the situation with the previously reported tetracationic cylinder involving a similar ligand. Linear dichroism (LD) data suggests that the dicopper cylinder binds in a different orientation from that of the tetracationic iron cylinder. Furthermore, the dicopper cylinder shows DNA-cleavage activity in the presence of peroxide. Of particular note is that the cylinder displays a marked and unusual ability to cleave both DNA strands at the same site, probably reflecting its dinuclear nature and possibly its mode of binding to the DNA.
Biological systems provide many intricate and elegant examples of the use of self-assembly through noncovalent recognition events to generate large functional arrays. Chemists have also been attempting to mimic this approach by using supramolecular interactions to construct a wide range of arrays of defined size and architecture (albeit on a smaller size scale). [1] Metallo-supramolecular chemistry in particular has been a popular and effective tool. [2] However, in common with other supramolecular systems synthesis of building blocks (in this case of the ligands) by the formation of covalent bonds places restrictions on the size of the architectures that have been generated. This situation represents a potential barrier to progress in this field. One approach to address this problem is to use multiple recognition events in sequence. Thus, an initial event generates a supramolecular structure which is then aggregated into a larger array in a second supramolecular event. [3±6] As in the assembly of ™simple∫ supramolecular structures, a challenge is to control the aggregation such that a discrete array (rather than a polymeric array) is obtained. We have been exploring the use of shape to control such aggregation and we recently reported the use of imine-based ligands to form arc-shaped double-helicates which aggregate into a discrete circular array as a result of their curved topography. [4] We have been investigating whether the same approach can be applied to form three dimensional (rather than planar) structures and herein we report the assembly of a supramolecular ball from commercially available components by this approach.We have shown that the reaction of ligand L with metal ions capable of tetrahedral coordination leads to a solution equilibrium of two dimeric isomers; a helicate (rac isomer) L a
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