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Published on: May 29, 2018
Solution-phase dynamics of DNA-stabilized metal quantum clusters: a chiroptical spectroscopic approach
Nanditha Rajeev1, Minnu Sunny1, Krishnadas Kumaranchira Ramankutty1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala P. O., Vithura, 695551, India. krishnadas@iisertvm.ac.in.
None:
DNA-stabilized metal quantum clusters are an emerging class of atomically precise chiral materials. Despite the inherent chirality and dynamic conformational landscape of DNA, chiroptical properties and structural dynamics of these clusters are poorly known. Here we present structural dynamics and dynamic chiral response of DNA-stabilized metal quantum clusters in solution probed using circular dichroism (CD) spectroscopy. CD spectroscopy reveals that the stacking and helicity of the orientation of nucleobases of the DNA ligands in these clusters are significantly different from those of the unbound DNA ligands. Our study reveals temperature-dependent, reversible, dynamic chiral response of these clusters in solution. No chirality inversion was observed for these clusters across a wide range of temperatures, indicating that these clusters are structurally robust which is in contrast to what one would expect from the dynamic nature of their DNA ligands. We hope that our work will stimulate further efforts to unravel the structural dynamics and its implications on the chiroptical properties of this new class of atomically precise matter.
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To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...

