Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Five-Spin Copper(II) Nitroxide Complex with Apparently Compressed Octahedral Geometry: Design, Synthesis, and Magnetostructural Studies. / Veber, Sergey L.; Tumanov, Sergey V.; Fokin, Sergey V. и др.
в: Crystal Growth and Design, Том 23, № 2, 01.02.2023, стр. 1057-1065.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Five-Spin Copper(II) Nitroxide Complex with Apparently Compressed Octahedral Geometry: Design, Synthesis, and Magnetostructural Studies
AU - Veber, Sergey L.
AU - Tumanov, Sergey V.
AU - Fokin, Sergey V.
AU - Tolstikov, Svyatoslav E.
AU - Sobenina, Lyubov’ N.
AU - Romanenko, Galina V.
AU - Bogomyakov, Artem S.
AU - Morozov, Vitaly A.
AU - Trofimov, Boris A.
AU - Ovcharenko, Victor I.
AU - Fedin, Matvey V.
N1 - This work was funded by the Russian Science Foundation Grant No. 22-13-00376 (EPR and FTIR study) and Grant No. 18-13-00380 (single-crystal XRD and magnetometry).
PY - 2023/2/1
Y1 - 2023/2/1
N2 - Multispin Cu(II)-nitroxide compounds have attracted significant interest in the field of molecular magnetism; however, complexes involving more than three spins in a single molecule have rarely been reported. In this work we describe the synthesis and detailed physicochemical study of the solvated six-coordinated five-spin complex [CuL2] (L = 2,2′-(1H-pyrrole-2,5-diyl)bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl)). This complex features a tridentate meridional coordination of the biradical L, resulting in an exchange-coupled cluster of four radical and one Cu(II) spin. The structural and magnetic properties of [CuL2] have been thoroughly investigated using single-crystal X-ray diffraction (XRD), SQUID magnetometry, electron paramagnetic resonance (EPR), Fourier-transform infrared (FTIR) spectroscopy, and quantum chemical calculations (QCC). An apparently compressed octahedral coordination geometry has been found by XRD, which, however, stems from the superposition of two isomeric structures of elongated octahedral CuN2O4 units. Neither X-ray nor FTIR has revealed any structural transitions in [CuL2] at 8-300 K, whereas the magnetic behavior studied by magnetometry and QCC is governed by temperature-dependent populations of high-spin multiplets. EPR spectroscopy revealed a drastic temperature dependence of the line width in [CuL2], which changes by almost 2 orders of magnitude within 4-300 K. A comparison with EPR and QCC data for close-structure four- and three-spin analogues has revealed an interplay of the temperature-dependent population of high-spin multiplets and intermolecular exchange interactions, which govern the line width in such systems.
AB - Multispin Cu(II)-nitroxide compounds have attracted significant interest in the field of molecular magnetism; however, complexes involving more than three spins in a single molecule have rarely been reported. In this work we describe the synthesis and detailed physicochemical study of the solvated six-coordinated five-spin complex [CuL2] (L = 2,2′-(1H-pyrrole-2,5-diyl)bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl)). This complex features a tridentate meridional coordination of the biradical L, resulting in an exchange-coupled cluster of four radical and one Cu(II) spin. The structural and magnetic properties of [CuL2] have been thoroughly investigated using single-crystal X-ray diffraction (XRD), SQUID magnetometry, electron paramagnetic resonance (EPR), Fourier-transform infrared (FTIR) spectroscopy, and quantum chemical calculations (QCC). An apparently compressed octahedral coordination geometry has been found by XRD, which, however, stems from the superposition of two isomeric structures of elongated octahedral CuN2O4 units. Neither X-ray nor FTIR has revealed any structural transitions in [CuL2] at 8-300 K, whereas the magnetic behavior studied by magnetometry and QCC is governed by temperature-dependent populations of high-spin multiplets. EPR spectroscopy revealed a drastic temperature dependence of the line width in [CuL2], which changes by almost 2 orders of magnitude within 4-300 K. A comparison with EPR and QCC data for close-structure four- and three-spin analogues has revealed an interplay of the temperature-dependent population of high-spin multiplets and intermolecular exchange interactions, which govern the line width in such systems.
UR - https://www.scopus.com/inward/record.url?eid=2-s2.0-85146539566&partnerID=40&md5=28031ed4f05cad9c42c035b7b7329623
UR - https://www.mendeley.com/catalogue/0d3d02c8-117b-3cb1-9341-0fbc9d39a8e4/
U2 - 10.1021/acs.cgd.2c01201
DO - 10.1021/acs.cgd.2c01201
M3 - Article
VL - 23
SP - 1057
EP - 1065
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 2
ER -
ID: 49728404