Abstract
Methods for the synthesis of binuclear [Cu(hfac)2LEt]2and tetranuclear [[Cu(hfac)2]4(LEt)2] heterospin compounds based on copper hexafluoroacetylacetonate [Cu(hfac)2] and 2-(4-ethylpyridin-3-yl)-4,5-bis(spirocyclopentyl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LEt), were developed. The crystals of the complexes are elastic and do not crash during repeated cooling–heating cycles. It was found that a singlet–triplet conversion occurred in all of the {Cu(II)–O•–N<} exchange clusters in the molecules of the binuclear [Cu(hfac)2LEt]2which led to spin coupling with cooling. The transition occurred in a wide temperature range with a maximum gradient ΔχT at ≈180 K. The structural transformation of the crystals takes place at T < 200 K and is accompanied by the lowering of symmetry from monoclinic to triclinic, twinning, and a considerable shortening of the Cu–ONO distance (2.19 and 1.97 Å at 295 and 50 K, respectively). For the tetranuclear [[Cu(hfac)2]4(LEt)2], two structural transitions were recorded (at ≈154 K and ≈118 K), which led to a considerable change in the spatial position of the Et substituent in the nitronyl nitroxyl fragment. The low-temperature process was accompanied by a spin transition recorded as a hysteresis loop on the χT(T) curve during the repeated cooling–heating cycles (T½↑ = 122 K, T½↓ = 115 K). This transition is unusual because it causes spin coupling in half of all of the {>N–•O–Cu2+} terminal exchange clusters, leading to spin compensation for only two paramagnetic centers of the six centers in the molecule.
Original language | English |
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Article number | 285 |
Number of pages | 13 |
Journal | Crystals |
Volume | 9 |
Issue number | 6 |
DOIs | |
Publication status | Published - 1 Jun 2019 |
Keywords
- Cu(II) complexes
- Magnetostructural correlations
- Nitroxides
- Phase transitions
- Spin crossover
- DESIGN
- LN
- ANOMALIES
- CU-II COMPLEXES
- COPPER(II)
- phase transitions
- CRYSTAL
- spin crossover
- magnetostructural correlations
- nitroxides
- CHAIN
- LIGANDS
- MAGNETIC-PROPERTIES