TY - JOUR
T1 - Heterometallic {Fe18M6} (M = Y, Gd, Dy) pivalate wheels display solvent-induced polymorphism
AU - Podgornii, Daniel
AU - Amombo Noa, Francoise M.
AU - Van Leusen, Jan
AU - McKenzie, Christine J.
AU - Öhrström, Lars
AU - Kögerler, Paul
AU - Baca, Svetlana G.
N1 - Funding Information:
This work in part was supported by State Programs of the National Agency for Research and Development of R. Moldova 20.80009.5007.15 (project “Implementation of crystal engineering approach and X-ray crystallography for design and creation of hybrid organic/inorganic materials with advanced physical and biologically active functions”). S.G.B. is grateful to the Alexander von Humboldt Foundation for a Georg Forster Research Award and the Swedish Institute for financial support under the Visby Program. C.J.M. is grateful to the Carlsberg Foundation for funding (grant CF15-0675) for the single crystal X-ray diffractometer. Authors thank Jürg Hauser for collecting X-ray data sets for 3a .
Publisher Copyright:
© 2022 The Authors. Published by American Chemical Society.
PY - 2022/9/7
Y1 - 2022/9/7
N2 - A new series of heterometallic wheels, isolated as [Fe18M6(piv)12(Htea)18(tea)6(N3)6]·n(solvent) (MIII = Y (1a, 1b), Gd (2a, 2b), and Dy (3a, 3b); Hpiv = pivalic acid, H3tea = triethanolamine), forms by the reaction of trinuclear μ3-oxo-linked or hexanuclear μ-OH-linked Fe(III) pivalate clusters with rare earth nitrates, H3tea, and azide ligands in MeOH/MeCN or EtOH/MeCN media under ultrasonic irradiation. Single-crystal X-ray diffraction showed that wheels 1a-3a prepared from MeOH/MeCN solutions crystallize in the triclinic space group P1¯ and have Ci symmetry, whereas wheels 1b-3b received from EtOH/MeCN solution crystallize in the trigonal space group R3¯ and have C3i symmetry. Magnetic studies reveal medium antiferromagnetic exchange interactions within the Fe3 trimeric unit (with the exchange coupling parameters of JFe3 = -13.1 cm-1 for 1a, JFe3 = -11.6 cm-1 for 1b) and weak intermolecular antiferromagnetic exchange interactions (λmf = -0.366 mol cm-3 and -0.368 mol cm-3 (zJmf = -0.19 cm-1), respectively). This leads to spin ground states of S = 5/2 for each {Fe3} unit. Substitution of diamagnetic Y(III) centers by paramagnetic Ln(III) centers (in 2a/2b by Gd(III) and in 3a/3b by Dy(III) centers) results in ferromagnetic exchange interactions between the Fe(III) and Ln(III) centers in addition to the predominant antiferromagnetic Fe···Fe interactions in 1a/1b.
AB - A new series of heterometallic wheels, isolated as [Fe18M6(piv)12(Htea)18(tea)6(N3)6]·n(solvent) (MIII = Y (1a, 1b), Gd (2a, 2b), and Dy (3a, 3b); Hpiv = pivalic acid, H3tea = triethanolamine), forms by the reaction of trinuclear μ3-oxo-linked or hexanuclear μ-OH-linked Fe(III) pivalate clusters with rare earth nitrates, H3tea, and azide ligands in MeOH/MeCN or EtOH/MeCN media under ultrasonic irradiation. Single-crystal X-ray diffraction showed that wheels 1a-3a prepared from MeOH/MeCN solutions crystallize in the triclinic space group P1¯ and have Ci symmetry, whereas wheels 1b-3b received from EtOH/MeCN solution crystallize in the trigonal space group R3¯ and have C3i symmetry. Magnetic studies reveal medium antiferromagnetic exchange interactions within the Fe3 trimeric unit (with the exchange coupling parameters of JFe3 = -13.1 cm-1 for 1a, JFe3 = -11.6 cm-1 for 1b) and weak intermolecular antiferromagnetic exchange interactions (λmf = -0.366 mol cm-3 and -0.368 mol cm-3 (zJmf = -0.19 cm-1), respectively). This leads to spin ground states of S = 5/2 for each {Fe3} unit. Substitution of diamagnetic Y(III) centers by paramagnetic Ln(III) centers (in 2a/2b by Gd(III) and in 3a/3b by Dy(III) centers) results in ferromagnetic exchange interactions between the Fe(III) and Ln(III) centers in addition to the predominant antiferromagnetic Fe···Fe interactions in 1a/1b.
U2 - 10.1021/acs.cgd.2c00620
DO - 10.1021/acs.cgd.2c00620
M3 - Journal article
AN - SCOPUS:85137408321
VL - 22
SP - 5526
EP - 5534
JO - Crystal Growth & Design
JF - Crystal Growth & Design
SN - 1528-7483
IS - 9
ER -