A family
of wheel-shaped charge-neutral heterometallic {FeIII4LnIII2}- and {FeIII18MIII6}-type coordination clusters demonstrates
the intricate interplay of solvent effects and structure-directing
roles of semiflexible bridging ligands. The {Fe4Ln2}-type compounds [Fe4Ln2(O2CCMe3)6(N3)4(Htea)4]·2(EtOH), Ln = Dy (1a), Er (1b), Ho (1c); [Fe4Tb2(O2CCMe3)6(N3)4(Htea)4] (1d); [Fe4Ln2(O2CCMe3)6(N3)4(Htea)4]·2(CH2Cl2), Ln = Dy (2a), Er (2b); [Fe4Ln2(O2CCMe3)4(N3)6(Htea)4]·2(EtOH)·2(CH2Cl2), Ln =
Dy (3a), Er (3b) and the {Fe18M6}-type compounds [Fe18M6(O2CCHMe2)12(Htea)18(tea)6(N3)6]·n(solvent),
M = Dy (4, 4a), Gd (5), Tb
(6), Ho (7), Sm (8), Eu (9), and Y (10) form in ca. 20–40% yields
in direct reaction of trinuclear FeIII pivalate or isobutyrate
clusters, lanthanide/yttrium nitrates, and bridging triethanolamine
(H3tea) and azide ligands in different solvents: EtOH for
the smaller {Fe4Ln2} wheels and MeOH/MeCN or
MeOH/EtOH for the larger {Fe18M6} wheels. Single-crystal
X-ray diffraction analyses revealed that 1–3 consist of planar centrosymmetric hexanuclear clusters built
from FeIII and LnIII ions linked by an array
of bridging carboxylate, azide, and aminopolyalcoholato-based ligands
into a cyclic structure with a cavity, and with distinct sets of crystal
solvents (2 EtOH per formula unit in 1a–c, 2 CH2Cl2 in 2, and 2
EtOH and 2 CH2Cl2 in 3). In 4–10, the largest 3d/4f wheels currently
known, nearly linear Fe3 fragments are joined via mononuclear
Ln/Y units by a set of isobutyrates and amino alcohol ligands into
virtually planar rings. The magnetic properties of 1–10 reveal slow magnetization relaxation for {Fe4Tb2} (1d) and slow relaxation for {Fe4Ho2} (1c), {Fe18Dy6} (4), and {Fe18Tb6} (6).