Keplerates are molecules that contain metal polyhedra that describe both Platonic and Archimedean solids; new copper keplerates are reported, with physical studies indicating that even where very high molecular symmetry is found, the low‐temperature physics does not necessarily reflect this symmetry.

Abstract. We discuss the magnetocaloric properties of gadolinium containing magnetic molecules which potentially could be used for sub-Kelvin cooling. We show that a degeneracy of a singlet ground state could be advantageous in order to support adiabatic processes to low temperatures and simultaneously minimize disturbing dipolar interactions. Since the Hilbert spaces of such spin systems assume very large dimensions we evaluate the necessary thermodynamic observables by means of the Finite-Temperature Lanczos Method.

Magnetization, specific heat, and electron spin resonance (ESR) measurements are carried out to clarify the low-energy excitations for the S = 1/2 polyhedral clusters {Mo72V30} and {W72V30}. The clusters provide unique model systems of Kagomé network on a quasi-sphere. The linear field variation of magnetization at low temperatures indicates that the ground state is singlet for both clusters. The temperature and the magnetic field dependence of specific heat shows a distinct difference between two clusters with differing structural symmetries. In {W72V30} with Ih symmetry, the existence of the several tens of low-energy singlet excited states below the lowest triplet excited state is revealed. The specific heat of the slightly distorted {Mo72V30} with D5h symmetry leads to a drastic decrease of the singlet contribution, which is consistent with the partial lifting of the frustration and the decrease of degenerated low-energy states. The singlet excitation existence is confirmed further by the temperature dependence of the ESR spectra. Comprehensive experimental studies have demonstrated unique low-energy excitations of the spherical Kagomé networks and their sensitivity to the cluster symmetry.

Two families of copper lanthanide phosphonate clusters have been obtained through reaction of [Cu2(O2C(t)Bu)4(HO2C(t)Bu)2] and either Ln(NO3)3·nH2O or [Ln2(O2C(t)Bu)6(HO2C(t)Bu)6] and tert-butylphosphonic acid or an amino-functionalized phosphonic acid. The clusters, with general formula [Cu(MeCN)4][Cu3Ln9(μ3-OH)7(O3P(t)Bu)6(O2C(t)Bu)15] and [Cu6Ln6(μ3-OH)6(O3PC(NH2)Me2)6(O2C(t)Bu)12], were structurally characterized through single crystal X-ray diffraction and possess highly symmetric metal cores with approximately C3v and D3h point symmetry, respectively. We have investigated the possible application of the isotropic analogues in magnetic cooling, where we were able to observe that up to around 70% of the theoretical magnetic entropy change is obtained. Simulation of the magnetic data shows antiferromagnetic coupling between the spin centers, which explains the magnetic entropy value observed.