Short but Weak: The Z-DNA lone-pair...Pi Conundrum Challenges Standard Carbon Van der Waals Radii
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F20%3A00116488" target="_blank" >RIV/00216224:14310/20:00116488 - isvavai.cz</a>
Result on the web
<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/ange.202004201" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/ange.202004201</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/anie.202004201" target="_blank" >10.1002/anie.202004201</a>
Alternative languages
Result language
angličtina
Original language name
Short but Weak: The Z-DNA lone-pair...Pi Conundrum Challenges Standard Carbon Van der Waals Radii
Original language description
Current interest in lone-pair center dot center dot center dot pi (lp center dot center dot center dot pi) interactions is gaining momentum in biochemistry and (supramolecular) chemistry. However, the physicochemical origin of the exceptionally short (ca. 2.8 angstrom) oxygen-to-nucleobase plane distances observed in prototypical Z-DNA CpG steps remains unclear. High-level quantum mechanical calculations, including SAPT2 + 3 interaction energy decompositions, demonstrate that lp center dot center dot center dot pi contacts do not result from n ->pi* orbital overlaps but from weak dispersion and electrostatic interactions combined with stereochemical effects imposed by the locally strained structural context. They also suggest that the carbon van der Waals (vdW) radii, originally derived for sp(3) carbons, should not be used for smaller sp(2) carbons attached to electronwithdrawing groups. Using a more adapted carbon vdW radius results in these lp center dot center dot center dot pi contacts being no longer of the sub-vdW type. These findings challenge the whole lp center dot center dot center dot pi concept that refers to elusive orbital interactions that fail to explain short interatomic contact distances.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10603 - Genetics and heredity (medical genetics to be 3)
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Angewandte Chemie International Edition
ISSN
1433-7851
e-ISSN
1521-3773
Volume of the periodical
59
Issue of the periodical within the volume
38
Country of publishing house
DE - GERMANY
Number of pages
8
Pages from-to
16553-16560
UT code for WoS article
000548319500001
EID of the result in the Scopus database
2-s2.0-85087864327