Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3
DFT-D3 calculations based on structural X-ray diffraction data obtained for 3-oxo-camphorsulfonyl imine (<b>1</b>), camphorsulfonyl chloride (<b>2</b>) and seven camphor sulfonimines (O<sub>2</sub>SNC<sub>10</sub>H<sub>13</sub>NR, <b>...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-10-01
|
| Series: | Crystals |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4352/13/10/1499 |
| _version_ | 1797574194064523264 |
|---|---|
| author | Joana Pais da Costa Maria Fernanda Nascimento Neves de Carvalho Adelino Moura Galvão |
| author_facet | Joana Pais da Costa Maria Fernanda Nascimento Neves de Carvalho Adelino Moura Galvão |
| author_sort | Joana Pais da Costa |
| collection | DOAJ |
| description | DFT-D3 calculations based on structural X-ray diffraction data obtained for 3-oxo-camphorsulfonyl imine (<b>1</b>), camphorsulfonyl chloride (<b>2</b>) and seven camphor sulfonimines (O<sub>2</sub>SNC<sub>10</sub>H<sub>13</sub>NR, <b>L<sup>1</sup></b>−<b>L<sup>7</sup></b>), from which <b>L<sup>2</sup></b> (R=4-OHC<sub>6</sub>H<sub>4</sub>), <b>L<sup>4</sup></b> (R=4-ClC<sub>6</sub>H<sub>4</sub>) and <b>L<sup>6</sup></b> (R=3,5-(CH<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) are synthesized and characterized in this work, provide information into the <i>intra</i>- and <i>inter</i>-molecular interactions with concomitant elucidation of the supramolecular arrangement of the compounds. The DFT-D3 calculations performed in small clusters of two or three molecular units reproduce the interactions observed via 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 (-NSO<sub>2</sub>) either to establish hydrogen bonds through oxygen atoms or non-classic oxygen–aliphatic hydrogen or non-bonding interactions (NBIs), which also involve sulfonyl oxygen atoms. Interestingly, the camphor sulfonimine compounds (<b>L<sup>2</sup></b>, <b>L<sup>3</sup></b>), having protic groups (R=C<sub>6</sub>H<sub>4</sub>X:X=OH, <b>L<sup>2</sup></b> or X=NH<sub>2</sub>, <b>L<sup>3</sup></b>) 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 <i>E</i> configuration with respect to the imine substituent (R). The study of the redox behavior of the compounds by cyclic voltammetry enables 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 (<b>L</b>) display appropriate binding atoms to coordinate transition metals. The results herein show that monodentate coordination through the nitrogen atom of the sulfonimine five-membered ring to the {Ag(NO<sub>3</sub>)} metal center is favored. When this imine nitrogen atom is not itself involved in the organic framework, DFT-D3 calculations show that the complexation does not affect the non-covalent interactions that are reproduced in the MOF structure. |
| first_indexed | 2024-03-10T21:19:26Z |
| format | Article |
| id | doaj.art-3836decd8006452796380e82f295f49e |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-10T21:19:26Z |
| publishDate | 2023-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-3836decd8006452796380e82f295f49e2023-11-19T16:10:05ZengMDPI AGCrystals2073-43522023-10-011310149910.3390/cryst13101499Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3Joana Pais da Costa0Maria Fernanda Nascimento Neves de Carvalho1Adelino Moura Galvão2Centro de Química Estrutural, Institute of Molecular Sciences and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Avenida António José de Almeida, n. 12, 1000-043 Lisboa, PortugalCentro de Química Estrutural, Institute of Molecular Sciences and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Avenida António José de Almeida, n. 12, 1000-043 Lisboa, PortugalCentro de Química Estrutural, Institute of Molecular Sciences and Departamento de Engenharia Química, Instituto Superior Técnico, Campus Taguspark, Universidade de Lisboa, Avenida Professor Doutor Cavaco Silva, 2744-016 Porto Salvo, PortugalDFT-D3 calculations based on structural X-ray diffraction data obtained for 3-oxo-camphorsulfonyl imine (<b>1</b>), camphorsulfonyl chloride (<b>2</b>) and seven camphor sulfonimines (O<sub>2</sub>SNC<sub>10</sub>H<sub>13</sub>NR, <b>L<sup>1</sup></b>−<b>L<sup>7</sup></b>), from which <b>L<sup>2</sup></b> (R=4-OHC<sub>6</sub>H<sub>4</sub>), <b>L<sup>4</sup></b> (R=4-ClC<sub>6</sub>H<sub>4</sub>) and <b>L<sup>6</sup></b> (R=3,5-(CH<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) are synthesized and characterized in this work, provide information into the <i>intra</i>- and <i>inter</i>-molecular interactions with concomitant elucidation of the supramolecular arrangement of the compounds. The DFT-D3 calculations performed in small clusters of two or three molecular units reproduce the interactions observed via 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 (-NSO<sub>2</sub>) either to establish hydrogen bonds through oxygen atoms or non-classic oxygen–aliphatic hydrogen or non-bonding interactions (NBIs), which also involve sulfonyl oxygen atoms. Interestingly, the camphor sulfonimine compounds (<b>L<sup>2</sup></b>, <b>L<sup>3</sup></b>), having protic groups (R=C<sub>6</sub>H<sub>4</sub>X:X=OH, <b>L<sup>2</sup></b> or X=NH<sub>2</sub>, <b>L<sup>3</sup></b>) 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 <i>E</i> configuration with respect to the imine substituent (R). The study of the redox behavior of the compounds by cyclic voltammetry enables 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 (<b>L</b>) display appropriate binding atoms to coordinate transition metals. The results herein show that monodentate coordination through the nitrogen atom of the sulfonimine five-membered ring to the {Ag(NO<sub>3</sub>)} metal center is favored. When this imine nitrogen atom is not itself involved in the organic framework, DFT-D3 calculations show that the complexation does not affect the non-covalent interactions that are reproduced in the MOF structure.https://www.mdpi.com/2073-4352/13/10/1499DFT-D3self-assemblycamphor sulfonimineX-ray diffractionredox propertiescomplexes |
| spellingShingle | Joana Pais da Costa Maria Fernanda Nascimento Neves de Carvalho Adelino Moura Galvão Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3 Crystals DFT-D3 self-assembly camphor sulfonimine X-ray diffraction redox properties complexes |
| title | Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3 |
| title_full | Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3 |
| title_fullStr | Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3 |
| title_full_unstemmed | Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3 |
| title_short | Camphor Sulfonimine Compounds: Bottom-Up Design of MOFs from Organic Frameworks Based on X-rays and DFT-D3 |
| title_sort | camphor sulfonimine compounds bottom up design of mofs from organic frameworks based on x rays and dft d3 |
| topic | DFT-D3 self-assembly camphor sulfonimine X-ray diffraction redox properties complexes |
| url | https://www.mdpi.com/2073-4352/13/10/1499 |
| work_keys_str_mv | AT joanapaisdacosta camphorsulfoniminecompoundsbottomupdesignofmofsfromorganicframeworksbasedonxraysanddftd3 AT mariafernandanascimentonevesdecarvalho camphorsulfoniminecompoundsbottomupdesignofmofsfromorganicframeworksbasedonxraysanddftd3 AT adelinomouragalvao camphorsulfoniminecompoundsbottomupdesignofmofsfromorganicframeworksbasedonxraysanddftd3 |