Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines

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...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autores principales: Dalila Rocco, Alessandro Prescimone, Edwin C. Constable, Catherine E. Housecroft
Formato: article
Lenguaje:EN
Publicado: MDPI AG 2021
Materias:
cobalt
3,2’:6’,3”-terpyridine
[1,1’-biphenyl]-4-yl substituents
2-dimensional network
coordination polymer
crystal structure
Organic chemistry
QD241-441
Acceso en línea:https://doaj.org/article/6e6a0363024a44dfb35dff00f17f89f9
Etiquetas: Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
id oai:doaj.org-article:6e6a0363024a44dfb35dff00f17f89f9
record_format dspace
spelling oai:doaj.org-article:6e6a0363024a44dfb35dff00f17f89f92021-11-11T18:22:14ZAdapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines10.3390/molecules262163371420-3049https://doaj.org/article/6e6a0363024a44dfb35dff00f17f89f92021-10-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6337https://doaj.org/toc/1420-3049Coordination 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.Dalila RoccoAlessandro PrescimoneEdwin C. ConstableCatherine E. HousecroftMDPI AGarticlecobalt3,2’:6’,3”-terpyridine[1,1’-biphenyl]-4-yl substituents2-dimensional networkcoordination polymercrystal structureOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6337, p 6337 (2021)
institution DOAJ
collection DOAJ
language EN
topic cobalt
3,2’:6’,3”-terpyridine
[1,1’-biphenyl]-4-yl substituents
2-dimensional network
coordination polymer
crystal structure
Organic chemistry
QD241-441
spellingShingle cobalt
3,2’:6’,3”-terpyridine
[1,1’-biphenyl]-4-yl substituents
2-dimensional network
coordination polymer
crystal structure
Organic chemistry
QD241-441
Dalila Rocco
Alessandro Prescimone
Edwin C. Constable
Catherine E. Housecroft
Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
description 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.
format article
author Dalila Rocco
Alessandro Prescimone
Edwin C. Constable
Catherine E. Housecroft
author_facet Dalila Rocco
Alessandro Prescimone
Edwin C. Constable
Catherine E. Housecroft
author_sort Dalila Rocco
title Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
title_short Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
title_full Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
title_fullStr Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
title_full_unstemmed Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines
title_sort adapting (4,4) networks through substituent effects and conformationally flexible 3,2’:6’,3”-terpyridines
publisher MDPI AG
publishDate 2021
url https://doaj.org/article/6e6a0363024a44dfb35dff00f17f89f9
work_keys_str_mv AT dalilarocco adapting44networksthroughsubstituenteffectsandconformationallyflexible3263terpyridines
AT alessandroprescimone adapting44networksthroughsubstituenteffectsandconformationallyflexible3263terpyridines
AT edwincconstable adapting44networksthroughsubstituenteffectsandconformationallyflexible3263terpyridines
AT catherineehousecroft adapting44networksthroughsubstituenteffectsandconformationallyflexible3263terpyridines
_version_ 1718431827693142016

Ejemplares similares