Indranil Sinha

The Journal retracts the article “6-Pyrazolylpurine as an artificial nucleobase for metal-mediated base pairing in DNA duplexes”

Two dinuclear metal complexes bearing the purine derivative 7-methyl-6-furylpurine (1b) as a ligand are reported. In [Ag₂(1b)₂(DMSO)₂](ClO₄)₂·DMSO and [Cu₂(1b)₂(NO₃)₂], two bridging purine derivatives coordinate the two metal ions via their N3 and N9 positions. In the silver(I) complex, the coordination environment of each metal ion is completed by a DMSO ligand, whereas an additional nitrato ligand coordinates to each copper(I) ion. The intramolecular Ag···Ag distance of 3.1069(5) Å is in agreement with the presence of a weak argentophilic interaction, whereas the Cu···Cu distance of 2.9382(4) Å is too long to be indicative of a cuprophilic interaction. The compounds represent the first examples of dinuclear complexes comprising two N3,N9-bridging purine derivatives without any additional bridging ligand.

The scholastic significance of supramolecular chemistry continues to grow with the recent development of catalytic transformations in confined space of supramolecular architectures. It has come a long way from a natural cavity containing molecules to modern smart materials capable of manipulating reaction pathways. The rise of self-assembled coordination complexes provided a diverse array of host structures. Starting from purely organic compounds to metalloligand surrogates, supramolecular host cavities were tuned according to the requirement of the reactions. The understanding of their participation in a reaction led to better usage of those assemblies for specific reaction sequences. Commencing from cyclodextrin, a wide range of organic molecules was used for cage-catalyzed organic transformations. However, difficulties in synthesis and a tedious purification procedure led chemists to choose a different pathway of metal–ligand coordination-driven self-assembly. The latter stood out as a potential replacement of the organic cages, overcoming the previous drawbacks. In the glut of different transition-metal assemblies used for catalytic transformations, many of them showed chemo- and stereoselective products. However, the small cavity size in some of them led to premature failure of the reaction. In that context, “molecular barrels” showed good efficacy for the catalytic reaction sequence. The large cavity size and bigger orifice for intake of the substrate and easy release of the product made them a better choice for catalysis. Additionally these are mostly used in aqueous media, which reinforces the idea of green and environmentally nonhazardous chemistry. In this Viewpoint, we discuss the use of metal–ligand coordination-driven self-assembled molecular containers used for catalysis with special emphasis on molecular barrels. This paper built on existing literature provides a thorough development of the fertile ground of the coordination architecture for catalysis and its future direction of propagation.

The mechanism of Fe-catalyzed cyclic carbonate formation of CO ₂ and internal epoxides was studied to identify design strategies for more efficient catalysts.

The synthesis and structure of [Ag(9-methyl-6-furylpurine)(NO₃)] n are reported. The title compound represents a rare example of a purine derivative metalated at all three endocyclic nitrogen atoms. It forms a two-dimensional coordination polymer comprising 14-membered trinuclear metallacycles. Density functional theory calculations helped to understand the metal-binding behavior of the 6-furylpurine moiety by showing the silver(I)-binding affinities of all three nitrogen donor atoms to be essentially identical under aqueous conditions.

A paramagnetic cobalt–SiH intermediate possessing the Co–(η ¹ -H–Si) moiety shows unusual Si–H bond activation studied by ENDOR, XRD and DFT.

The artificial nucleobase 6-pyrazol-1-yl-purine (6PP) has been investigated with respect to its usability in metal-mediated base pairing. As was shown by temperature-dependent UV spectroscopy, 6PP may form weakly stabilizing 6PP–Ag(I)–6PP homo base pairs. Interestingly, 6PP can be used to selectively recognize a complementary pyrimidine nucleobase. The addition of Ag(I) to a DNA duplex comprising a central 6PP:C mispair (C = cytosine) leads to a slight destabilization of the duplex. In contrast, a stabilizing 6PP–Ag(I)–T base pair is formed with a complementary thymine (T) residue. It is interesting to note that 6PP is capable of differentiating between the pyrimidine moieties despite the fact that it is not as sterically crowded as 6-(3,5-dimethylpyrazol-1-yl)purine, an artificial nucleobase that had previously been suggested for the recognition of nucleic acid sequences via the formation of a metal-mediated base pair. Hence, the additional methyl groups of 6-(3,5-dimethylpyrazol-1-yl)purine may not be required for the specific recognition of the complementary nucleobase.

We report the C-metalation of 6-furylpurine with Pt²⁺, Pd²⁺, and Hg²⁺. The ligand binds the metal ions in a bidentate fashion, involving the N7 purine atom and one of the furyl carbon atoms. The regioselectivity is determined by the metal ion. Pt²⁺ and Pd²⁺ coordinate the furyl moiety in its β position and Hg²⁺ in its electronically preferred α position.