Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
Coordination networks formed between Co(NCS)<sub>2</sub> and 4’-substituted-[1,1’-biphenyl]-4-yl-3,2’:6’,3”-terpyridines in which the 4’-group is Me (<b>1</b>), H (<b>2</b>), F (<b>3</b>), Cl (<b>4</b>) or Br (<b>5</b>) are repo...
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| Autores principales: | , , , |
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| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
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| Materias: | |
| Acceso en línea: | https://doaj.org/article/6e6a0363024a44dfb35dff00f17f89f9 |
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| Sumario: | Coordination networks formed between Co(NCS)<sub>2</sub> and 4’-substituted-[1,1’-biphenyl]-4-yl-3,2’:6’,3”-terpyridines in which the 4’-group is Me (<b>1</b>), H (<b>2</b>), F (<b>3</b>), Cl (<b>4</b>) or Br (<b>5</b>) are reported. [Co(<b>1</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4.5<i>n</i>CHCl<sub>3</sub>, [Co(<b>2</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4.3<i>n</i>CHCl<sub>3</sub>, [Co(<b>3</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4<i>n</i>CHCl<sub>3</sub>, [Co(<b>4</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>, and [Co(<b>5</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·<i>n</i>CHCl<sub>3</sub> are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2’:6’,3”-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co(<b>1</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4.5<i>n</i>CHCl<sub>3</sub>, [Co(<b>2</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4.3<i>n</i>CHCl<sub>3</sub>, [Co(<b>3</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4<i>n</i>CHCl<sub>3</sub>, cone-like arrangements of [1,1’-biphenyl]-4-yl units pack through pyridine…arene π-stacking, whereas Cl…π interactions are dominant in the packing in [Co(<b>4</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub>.</i> The introduction of the Br substituent in ligand <b>5</b> switches off both face-to-face π-stacking and halogen…π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers <b>1</b>–<b>3</b> are structurally similar and the lattice accommodates CHCl<sub>3</sub> molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co(<b>3</b>)<sub>2</sub>(NCS)<sub>2</sub>]<i><sub>n</sub></i>·4<i>n</i>CHCl<sub>3</sub> can be reversibly removed. |
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