Computational design of three Cu-induced triangular pyrimidines-based DNA motifs with improved conductivity

Novel DNA triangular pyrimidine derivatives are designed by metal-decoration through replacement of H-by-Cu in the Watson-Crick hydrogen bond region. The DFT method is used to examine the coordination of triangle-arranged Cu with three pyrimidines in nonplanar three-bladed turbine geometries. The Cu···Cu cuprophilic bonds are ascribed to the partially occupied d orbitals without direct molecular orbital (MO) interactions. Four-center bonds depend on Cu-N/O bonds, which are contributed by p orbitals of N/O atoms along or perpendicular to the bond axis. The activity of frontier MOs is modulated leading to the decrease of gaps, ionization potentials (IPs) and electron affinities (EAs) desired for the improvement of conductivity. The hole trapping ability is assured by virtue of the spin density distributed on Cu. The single electron density is located averagely on π orbitals of three aromatic base rings. There’s paramagnetic electron delocalization on the inner d orbitals of triangle region. The analysis of electron localization function ELF-π and electrostatic potential maps reveals that the outer strong π-π stacking interaction together with the inner d orbital channel enable effective transduction of electrical signals along the Cu-DNA nanowires. The 3Cu-induced triangular pyrimidines have great potential applications as structural motifs of molecular electronic devices.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author