Costa, J.P.; Carvalho, M.F.N.N.; Galvão, A.M. Camphor Sulfonimine Compounds: Bottom-up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3. Crystals2023, 13, 1499.
Costa, J.P.; Carvalho, M.F.N.N.; Galvão, A.M. Camphor Sulfonimine Compounds: Bottom-up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3. Crystals 2023, 13, 1499.
Costa, J.P.; Carvalho, M.F.N.N.; Galvão, A.M. Camphor Sulfonimine Compounds: Bottom-up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3. Crystals2023, 13, 1499.
Costa, J.P.; Carvalho, M.F.N.N.; Galvão, A.M. Camphor Sulfonimine Compounds: Bottom-up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3. Crystals 2023, 13, 1499.
Abstract
DFT-D3 calculations based on structural X-ray diffraction data obtained for 3-oxo-camphorsulfonyl imine (1), camphorsulfonyl chloride (2) and seven camphor sulfonimines (O2SNC10H13NR, L1-L7) from which L2 (R=4-OHC6H4), L4 (R=4-ClC6H4) and L6 (R=3,5-(CH3)2C6H3) are new, provide information into the intra and inter molecular interactions with concomitant elucidation of the supramolecular arrangement of the compounds. The DFT D3 calculations performed in small clusters of 2 or 3 molecular units reproduce the interactions observed by X-ray analyses showing that as a general trend the structural arrangement of the molecules is driven by electronic rather than by packing parameters.
In all compounds the self-assembly of 3D structures involves the sulfonyl imine group ( NSO2) either to establish hydrogen bonds, through the oxygen atoms or non-classic oxygen-aliphatic hydrogen or non-bonding interactions (NBI) which also involve the sulfonyl oxygens. Interestingly, the camphor sulfonimine compounds (L2, L3) having protic groups (R=C6H4X: X=OH, L2 or X=NH2, L3) at the aromatic imine substituents (=NR) present an extra π-π stacking which is absent in the other compounds aromatic derivatives.
The X-ray analysis shows that all the reported camphor sulfonimine compounds display the E configuration with respect to the imine substituent (R).
The study of the redox behavior of the compounds by cyclic voltammetry allows an insight into the solution properties of the compounds and the rationalization of the molecular interactions that stand in the solid and solution states.
Camphor sulfonimine compounds (L) display appropriate binding atoms to coordinate transition metals. The herein results show that monodentate coordination through the nitrogen atom of the sulfonimine 5-membered ring to the {Ag(NO3)} metal center is favored. When this imine nitrogen atom is not itself involved in the Organic Framework DFT-D3 calculations shows that the complexation does not affect the non-covalent interactions that are reproduced in the MOF structure.
Chemistry and Materials Science, Theoretical Chemistry
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