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Controlling molecular magnetic anisotropy via structural engineering is delicate and fascinating, especially for singlemolecule magnets (SMMs). Herein a family of dysprosium single-ion magnets (SIMs) sitting in pentagonal bipyramid geometry have been synthesized with the variable-size terminal ligands and counter anions, through which the subtle coordination geometry of Dy(III) can be finely tuned based on the size effect. The effective energy barrier (Ueff) successfully increases from 439 K to 632 K and the magnetic hysteresis temperature (under a 200 Oe/s sweep rate) raises from 11 K to 24 K. Based on the crystal-field theory, a semi-quantitative magneto-structural correlation deducing experimentally for the first time is revealed that the Ueff is linearly proportional to the structural-related value 2 0 corresponding to the axial coordination bond lengths and the bond angles. Through the evaluation of the remanent magnetization from hysteresis, quantum tunneling of magnetization (QTM) is found to exhibit negative correlation with the structural-related value Stun corresponding to the axial coordination bond angles.

Spin-crossover (SCO) metal-organic cages capable of switching between high-spin and low-spin states have the potential to be used as magnetic sensors and switches. Variation of the donor strength of heterocyclic aldehyde subcomponents in imine-based ligands can tune the ligand field for a Fe II center, which results in both homoleptic and heteroleptic cages with diverse SCO behaviors. The tetrahedral SCO cage built from 1-methyl-1H-imidazole-2-carbaldehyde is capable of encapsulating various guests, which stabilize different cage spin states depending on guest size. Conversely, the SCO tetrahedron exhibits different affinities for guests in different spin states, which is inferred to result from subtle structural differences of the cavity caused by the change in metal center spin state. Examination of SCO thermodynamics across a series of host-guest complexes enabled sensitive probing of guest fit to the host cavity, providing information complementary to binding-constant determination.

Biomolecular systems show how host–guest binding can induce changes in molecular behavior, which in turn impact the functions of the system. Here we report an artificial host–guest system where dynamic adaptation during guest binding alters both host conformation and guest dynamics. The self-assembled cage host employed here possesses concave walls and a chirotopic cavity. Complementarity between the curved surfaces of fullerenes and the inner surface of the host cavity leads the host to reconfigure stereochemically in order to bind these guests optimally. The curved molecule corannulene undergoes rapid bowl-to-bowl inversion at room temperature. Its inversion barrier is increased upon binding, however, and increased further upon formation of a ternary complex, where corannulene and a cycloalkane are both bound together. The chiral nature of the host also leads to clear differences in the NMR spectra of ternary complexes involving corannulene and one or the other enantiomer of a chiral guest, which enables the determination of enantiomeric excess by NMR.

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