A C-nucleoside with 6-phenyl-1H-carbazole as the base moiety has been synthesized and incorporated in the middle of an oligonucleotide. Mercuration of this modified residue at positions 1 and 8 gave the first example of an oligonucleotide featuring a monofacial dinuclear organometallic nucleobase. The dimercurated oligonucleotide formed stable duplexes with unmodified oligonucleotides placing either cytosine, guanine, or thymine opposite to the organometallic nucleobase. A highly stabilizing (ΔT =7.3 °C) Hg -mediated base pair was formed with thymine. According to DFT calculations performed at the PBE0DH level of theory, this base pair is most likely dinuclear, with the two Hg ions coordinated to O2 and O4 of the thymine base.
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Article Synopsis
- The paper discusses a new method for calculating nuclear magnetic resonance shielding constants using hybrid multiconfigurational short-range density functional theory (srDFT), which includes a special case of Hartree-Fock srDFT (HF-srDFT).
- It compares the performance of this new method, called CAS-srDFT, against traditional approaches like DFT and CASSCF using adenine and thymine as test cases, showing that CAS-srDFT generally provides the most accurate results.
- The findings suggest that incorporating exact exchange is crucial for accurately predicting shielding constants, especially in systems with significant static correlation like transition metal complexes, where CAS-srDFT outperforms previous methods.
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