Copper(I) complexes of bipyridine and terpyridine with fluorous tails and the formation of crystalline materials with fluorous layers

Vedichi Madhu, Yael Diskin-Posner, Ronny Neumann

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Copper(I) complexes with perfluorinated tails, (CuIL 2AcN)BF4 and (CuIL3AcN)BF 4, where L2 = 6,6′-bis(perfluorohexyl)-2,2′: 6′,2′-terpyridine and L3 = 6,6′-bis(2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl)-2,2′-bipyridine and AcN = acetonitrile, were synthesized and their rather unique crystal structures were elucidated. (CuIL2AcN)BF4 crystallizes in a low-symmetry space group, P$\bar {1}$, with a very large unit cell that required synchrotron radiation to locate all atoms. The molecular structure of (CuIL2AcN)BF4 has an asymmetric tetrahedrally distorted square-planar coordination sphere around CuI. Eight similar but distinct molecular structures were found. The crystal packing of (Cu IL2AcN)(BF4) has a layered structure with a clear segregation between the terpyridine moieties and the fluorous chains. The terpyridine units are arranged in a "back to back" fashion and tilted 20-25° relative to the interlayer plane, and the layered structure is staggered with offsets of approximately 4 Å between layers. The molecular structure of (CuIL3AcN)(BF4) features a Y-shaped trigonal planar coordination sphere around copper(I). Comparison of the structure with analogous CuI(neocuproine)AcN showed that the fluorous tails with the CH2CH2 spacers basically have no effect on the bond lengths and angles to Cu1. The crystal structure of (CuIL3AcN)(BF4) shows a "herring bone" conformation with an approximately 96° angle in the CubipyAcN units. The "herring bone" conformation leads to an accordion-type fluorous layer. Copper(I) complexes of bipyridine (Y-shaped trigonal planar) and terpyridine (tetrahedrally distorted square-planar) with fluorous tails showed crystal packing with segregation of the aromatic units and the fluorous tails. Layered structures that are tilted in two different dimensions as well as "herring bone" structures with accordion-like fluorous layers were observed.

Original languageEnglish
Pages (from-to)1792-1796
Number of pages5
JournalEuropean Journal of Inorganic Chemistry
Issue number11
DOIs
Publication statusPublished - Apr 2011

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Molecular structure
Copper
Bone
Crystalline materials
Conformations
Crystal structure
Crystals
Bond length
Synchrotron radiation
Atoms
neocuproine
acetonitrile

Keywords

  • Copper
  • Electron-deficient compounds
  • Fluorous compounds
  • Ligand effects
  • Stacking interactions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Copper(I) complexes of bipyridine and terpyridine with fluorous tails and the formation of crystalline materials with fluorous layers. / Madhu, Vedichi; Diskin-Posner, Yael; Neumann, Ronny.

In: European Journal of Inorganic Chemistry, No. 11, 04.2011, p. 1792-1796.

Research output: Contribution to journalArticle

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abstract = "Copper(I) complexes with perfluorinated tails, (CuIL 2AcN)BF4 and (CuIL3AcN)BF 4, where L2 = 6,6′-bis(perfluorohexyl)-2,2′: 6′,2′-terpyridine and L3 = 6,6′-bis(2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl)-2,2′-bipyridine and AcN = acetonitrile, were synthesized and their rather unique crystal structures were elucidated. (CuIL2AcN)BF4 crystallizes in a low-symmetry space group, P$\bar {1}$, with a very large unit cell that required synchrotron radiation to locate all atoms. The molecular structure of (CuIL2AcN)BF4 has an asymmetric tetrahedrally distorted square-planar coordination sphere around CuI. Eight similar but distinct molecular structures were found. The crystal packing of (Cu IL2AcN)(BF4) has a layered structure with a clear segregation between the terpyridine moieties and the fluorous chains. The terpyridine units are arranged in a {"}back to back{"} fashion and tilted 20-25° relative to the interlayer plane, and the layered structure is staggered with offsets of approximately 4 {\AA} between layers. The molecular structure of (CuIL3AcN)(BF4) features a Y-shaped trigonal planar coordination sphere around copper(I). Comparison of the structure with analogous CuI(neocuproine)AcN showed that the fluorous tails with the CH2CH2 spacers basically have no effect on the bond lengths and angles to Cu1. The crystal structure of (CuIL3AcN)(BF4) shows a {"}herring bone{"} conformation with an approximately 96° angle in the CubipyAcN units. The {"}herring bone{"} conformation leads to an accordion-type fluorous layer. Copper(I) complexes of bipyridine (Y-shaped trigonal planar) and terpyridine (tetrahedrally distorted square-planar) with fluorous tails showed crystal packing with segregation of the aromatic units and the fluorous tails. Layered structures that are tilted in two different dimensions as well as {"}herring bone{"} structures with accordion-like fluorous layers were observed.",
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N2 - Copper(I) complexes with perfluorinated tails, (CuIL 2AcN)BF4 and (CuIL3AcN)BF 4, where L2 = 6,6′-bis(perfluorohexyl)-2,2′: 6′,2′-terpyridine and L3 = 6,6′-bis(2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl)-2,2′-bipyridine and AcN = acetonitrile, were synthesized and their rather unique crystal structures were elucidated. (CuIL2AcN)BF4 crystallizes in a low-symmetry space group, P$\bar {1}$, with a very large unit cell that required synchrotron radiation to locate all atoms. The molecular structure of (CuIL2AcN)BF4 has an asymmetric tetrahedrally distorted square-planar coordination sphere around CuI. Eight similar but distinct molecular structures were found. The crystal packing of (Cu IL2AcN)(BF4) has a layered structure with a clear segregation between the terpyridine moieties and the fluorous chains. The terpyridine units are arranged in a "back to back" fashion and tilted 20-25° relative to the interlayer plane, and the layered structure is staggered with offsets of approximately 4 Å between layers. The molecular structure of (CuIL3AcN)(BF4) features a Y-shaped trigonal planar coordination sphere around copper(I). Comparison of the structure with analogous CuI(neocuproine)AcN showed that the fluorous tails with the CH2CH2 spacers basically have no effect on the bond lengths and angles to Cu1. The crystal structure of (CuIL3AcN)(BF4) shows a "herring bone" conformation with an approximately 96° angle in the CubipyAcN units. The "herring bone" conformation leads to an accordion-type fluorous layer. Copper(I) complexes of bipyridine (Y-shaped trigonal planar) and terpyridine (tetrahedrally distorted square-planar) with fluorous tails showed crystal packing with segregation of the aromatic units and the fluorous tails. Layered structures that are tilted in two different dimensions as well as "herring bone" structures with accordion-like fluorous layers were observed.

AB - Copper(I) complexes with perfluorinated tails, (CuIL 2AcN)BF4 and (CuIL3AcN)BF 4, where L2 = 6,6′-bis(perfluorohexyl)-2,2′: 6′,2′-terpyridine and L3 = 6,6′-bis(2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl)-2,2′-bipyridine and AcN = acetonitrile, were synthesized and their rather unique crystal structures were elucidated. (CuIL2AcN)BF4 crystallizes in a low-symmetry space group, P$\bar {1}$, with a very large unit cell that required synchrotron radiation to locate all atoms. The molecular structure of (CuIL2AcN)BF4 has an asymmetric tetrahedrally distorted square-planar coordination sphere around CuI. Eight similar but distinct molecular structures were found. The crystal packing of (Cu IL2AcN)(BF4) has a layered structure with a clear segregation between the terpyridine moieties and the fluorous chains. The terpyridine units are arranged in a "back to back" fashion and tilted 20-25° relative to the interlayer plane, and the layered structure is staggered with offsets of approximately 4 Å between layers. The molecular structure of (CuIL3AcN)(BF4) features a Y-shaped trigonal planar coordination sphere around copper(I). Comparison of the structure with analogous CuI(neocuproine)AcN showed that the fluorous tails with the CH2CH2 spacers basically have no effect on the bond lengths and angles to Cu1. The crystal structure of (CuIL3AcN)(BF4) shows a "herring bone" conformation with an approximately 96° angle in the CubipyAcN units. The "herring bone" conformation leads to an accordion-type fluorous layer. Copper(I) complexes of bipyridine (Y-shaped trigonal planar) and terpyridine (tetrahedrally distorted square-planar) with fluorous tails showed crystal packing with segregation of the aromatic units and the fluorous tails. Layered structures that are tilted in two different dimensions as well as "herring bone" structures with accordion-like fluorous layers were observed.

KW - Copper

KW - Electron-deficient compounds

KW - Fluorous compounds

KW - Ligand effects

KW - Stacking interactions

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