Abstract
Dinuclear metal-mediated homo base pairs are interesting clusters with highly symmetric structures and significant stabilities. The geometric and electronic structures of G2M22+ (G = Guanine, M = Cu, Ag or Au) cluster ions were studied with quantum chemical calculations. The lowest-energy isomers of G2M22+ cluster ions have C2h symmetries with an approximately antiparallel alignment of two sets of N-M∙∙∙O groups being formed in the planar structures. The M-M distances are shorter than the sum of van der Waals radii of corresponding two homo coinage metal atoms, showing that metallophilic interactions significantly exist in these complexes. They have the large HOMO−LUMO gaps of about 5.80 eV at the DFT level and the bond dissociation energies of more than 5.60 eV at the DFT/B3LYP level, indicating that these cluster dications are highly stable. The second lowest-energy isomers stabilized by an approximately parallel alignment of one set of O-M-O group and one set of N-M-N group are found to be close to the lowest-energy isomers in energy. The barrier between the two isomers of G2M22+ cluster ions is significantly large, also showing that these lowest-energy isomers are very stable.
Highlights
Waals radii of corresponding two homo coinage metal atoms, showing that metallophilic interactions significantly exist in these complexes
It is interesting to pinpoint whether dinuclear coinage metal-mediated homo base pairs are stable and in which direction gold-mediated base pairs might deviate from the copper or silver analogues
The geometric and electronic structures of G2M22+ (G = Guanine, M = Cu, Ag or Au) cluster ions have been investigated with DFT approaches
Summary
Waals radii of corresponding two homo coinage metal atoms, showing that metallophilic interactions significantly exist in these complexes. They have the large HOMO−LUMO gaps of about 5.80 eV at the DFT level and the bond dissociation energies of more than 5.60 eV at the DFT/B3LYP level, indicating that these cluster dications are highly stable. Dinuclear CuII and HgII complexes containing an artificial nucleobase (9-ethyl-1, N6-ethenoadenine) have been prepared and their crystal structures have been determined by Mandal et al.[20,21,22] Their studies show that dinuclear T-HgII2-εA base pair has two sets of parallel M-N bonds with anionic ligands partially compensating the charge of metal ions. The calculated results for the G2M22+ complexes provide new aspects for chemical bonding of the coinage metals and help to find potential applications of metal-mediated base pairs complexes
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