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<p>Computational modeling of dihydropyrene derivatives bearing 4,4,5,5-tetramethyl-4,5-dihydro-1<i>H</i>-imidazol-1-oxyl-3-oxide (<b>1</b>), <i>tert</i>-butyl nitroxide (<b>2</b>), and fluorenyl (<b>3</b>) radical groups, as well as various substituents (H, CN, Me) at the C(15) and C(16) atoms was carried out in terms of the density functional theory (DFT) at the B3LYP-D3BJ/6-311++G(d,p) level and using the SA-CASSCF/NEVPT2 method. It was established that isomerization of compounds <b>3</b> is accompanied by a spin-state switchng, which manifests itself as a transition from the diamagnetic cyclic dihydropyrene (<i>dhp</i>) form to the paramagnetic open (cyclophanediene, <i>cpd</i>) one. Time-dependent DFT calculations of the electronic spectra of the <i>dhp</i> and <i>cpd</i> isomers of the compounds bearing fluorenyl groups revealed the presence of non-overlapping bands. The results obtained give grounds to expect that photo-controlled spin-state changes in dihydropyrenes <b>3</b> are feasible and these systems can be considered as molecular magnetic switches.</p>

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Magnetic properties of diradical dihydropyrene derivatives: a computational modeling

  • 期刊论文

  • 发表日期：

    2025年9月1日

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  • A. G. Starikov,
  • M. G. Chegerev,
  • A. A. Starikova,
  • V. I. Minkin

摘要

Computational modeling of dihydropyrene derivatives bearing 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-oxide (1), tert-butyl nitroxide (2), and fluorenyl (3) radical groups, as well as various substituents (H, CN, Me) at the C(15) and C(16) atoms was carried out in terms of the density functional theory (DFT) at the B3LYP-D3BJ/6-311++G(d,p) level and using the SA-CASSCF/NEVPT2 method. It was established that isomerization of compounds 3 is accompanied by a spin-state switchng, which manifests itself as a transition from the diamagnetic cyclic dihydropyrene (dhp) form to the paramagnetic open (cyclophanediene, cpd) one. Time-dependent DFT calculations of the electronic spectra of the dhp and cpd isomers of the compounds bearing fluorenyl groups revealed the presence of non-overlapping bands. The results obtained give grounds to expect that photo-controlled spin-state changes in dihydropyrenes 3 are feasible and these systems can be considered as molecular magnetic switches.