Synthesis and magnetic properties of stable radical derivatives carrying a phenylacetylene unit

Shogo Miyashiro, Tomoaki Ishii, Youhei Miura, Naoki Yoshioka

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A nitronyl nitroxide derivative, 2-phenylethynyl-4,4,5,5-tetramethyl-4,5-dihydro-1Himidazol- 1-oxyl-3-oxide (1), and two verdazyl derivatives carrying a phenylacetylene unit, 1,5-diphenyl-3-phenylethynyl-6-oxo-1,2,4,5-tetrazin-2-yl (2) and 1,5-diisopropyl-3-phenylethynyl- 6-oxo-1,2,4,5-tetrazin-2-yl (3), were synthesized and their packing structures were studied by X-ray crystallographic analysis and magnetically characterized in the solid state. While 1 and 3 had an isolated doublet spin state, 2 formed an antiferromagnetically coupled pair (2J/kB = -118 K). Density functional theory (DFT) calculations reveal that the spin density polarized in the phenyl group decreases as the dihedral angle between the phenyl ring and radical plane increases.

Original languageEnglish
Article number371
JournalMolecules
Volume23
Issue number2
DOIs
Publication statusPublished - 2018 Jan 1

Fingerprint

Oxides
Magnetic properties
X-Rays
magnetic properties
Derivatives
Dihedral angle
synthesis
Density functional theory
dihedral angle
density functional theory
solid state
X rays
oxides
rings
x rays
phenylacetylene
diphenyl

Keywords

  • Computational analysis
  • Magnetic property
  • Nitronyl nitroxide
  • Phenylacetylene
  • Stable radical
  • Verdazyl

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Synthesis and magnetic properties of stable radical derivatives carrying a phenylacetylene unit. / Miyashiro, Shogo; Ishii, Tomoaki; Miura, Youhei; Yoshioka, Naoki.

In: Molecules, Vol. 23, No. 2, 371, 01.01.2018.

Research output: Contribution to journalArticle

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N2 - A nitronyl nitroxide derivative, 2-phenylethynyl-4,4,5,5-tetramethyl-4,5-dihydro-1Himidazol- 1-oxyl-3-oxide (1), and two verdazyl derivatives carrying a phenylacetylene unit, 1,5-diphenyl-3-phenylethynyl-6-oxo-1,2,4,5-tetrazin-2-yl (2) and 1,5-diisopropyl-3-phenylethynyl- 6-oxo-1,2,4,5-tetrazin-2-yl (3), were synthesized and their packing structures were studied by X-ray crystallographic analysis and magnetically characterized in the solid state. While 1 and 3 had an isolated doublet spin state, 2 formed an antiferromagnetically coupled pair (2J/kB = -118 K). Density functional theory (DFT) calculations reveal that the spin density polarized in the phenyl group decreases as the dihedral angle between the phenyl ring and radical plane increases.

AB - A nitronyl nitroxide derivative, 2-phenylethynyl-4,4,5,5-tetramethyl-4,5-dihydro-1Himidazol- 1-oxyl-3-oxide (1), and two verdazyl derivatives carrying a phenylacetylene unit, 1,5-diphenyl-3-phenylethynyl-6-oxo-1,2,4,5-tetrazin-2-yl (2) and 1,5-diisopropyl-3-phenylethynyl- 6-oxo-1,2,4,5-tetrazin-2-yl (3), were synthesized and their packing structures were studied by X-ray crystallographic analysis and magnetically characterized in the solid state. While 1 and 3 had an isolated doublet spin state, 2 formed an antiferromagnetically coupled pair (2J/kB = -118 K). Density functional theory (DFT) calculations reveal that the spin density polarized in the phenyl group decreases as the dihedral angle between the phenyl ring and radical plane increases.

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KW - Phenylacetylene

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