Štěpánek, P., & Lantto, P. (2022). Unexpected NMR shieldings of sp- and sp 2 -hybridized carbon atoms in graphyne systems. Physical Chemistry Chemical Physics, 24(41), 25513–25521. https://doi.org/10.1039/D2CP03837D
Unexpected NMR shieldings of sp- and sp²-hybridized carbon atoms in graphyne systems
|Author:||Štěpánek, Petr1; Lantto, Perttu1|
1NMR Research unit, Faculty of Science, University of Oulu, Oulu, Finland
|Online Access:||PDF Full Text (PDF, 1.7 MB)|
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe2022110264116
Royal Society of Chemistry,
|Publish Date:|| 2022-11-02
Graphynes (GYs) are two-dimensional alloptropic forms of carbon consisting of periodically arranged sp- and sp2-hybridized carbon atoms in a planar structure. Graphynes can be formally created from graphene by inserting sp-hybridized carbon links into selected points of the graphene lattice. Depending on where the links are introduced, several forms of graphynes have been proposed with properties that make them potential candidates for new generation electronics or for applications in chemical processes. Since the applications of each form of GY depend on its structure, it is of interest to experimentally distinguish different forms of graphynes. In this paper we propose nuclear magnetic resonance (NMR) as a potential method of choice for such distinction. We computationally investigate on the DFT level the ¹³C-NMR chemical shifts for α-, β-, γ-, rhombic, and 6,6,12-graphynes, and α- and γ-graphdiynes. We perform the calculations both in periodic systems and with approximate finite models. The results show that NMR chemical shifts in graphynes are dependent on the structure and reflect the local bonding around the carbon nucleus. Interestingly, NMR shifts of several graphynes show anomalous values, differing significantly from shifts found in typical sp²-hybridized systems. We analyze these results in terms of local structural parameters and qualitatively investigate the possible origins of these anomalous NMR shifts. The results show that NMR is a viable method for determining the structure of graphynes and their finite precursor molecules.
PCCP. Physical chemistry chemical physics
|Pages:||25513 - 25521|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
116 Chemical sciences
114 Physical sciences
The authors acknowledge the financial support from the Academy of Finland (Grant 316180). The computational resources were provided by CSC – IT Center for Science (Espoo, Finland) and the Finnish Grid and Cloud Infrastructure project (persistent identifier urn:nbn:fi:research-infras-2016072533).
|Academy of Finland Grant Number:||
316180 (Academy of Finland Funding decision)
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