Good things come in small packages: For its moderate molecular weight, the metallostar complex [Fe{Gd₂L(H₂O)₄}₃]⁴⁻ (see picture; L is a bipyridine–poly(aminocarboxylate) derivative) displays exceptionally high proton relaxivity, which is explained in terms of a rigid supramolecular structure, two inner‐sphere water molecules with a near‐optimal exchange rate, and six efficiently relaxing Gd^III centers confined to a small molecular space.

The time correlation functions of the electronic spin components of a metal ion without orbital degeneracy in solution are computed. The approach is based on the numerical solution of the time-dependent Schrödinger equation for a stochastic perturbing Hamiltonian which is simulated by a Monte Carlo algorithm using discrete time steps. The perturbing Hamiltonian is quite general, including the superposition of both the static mean crystal field contribution in the molecular frame and the usual transient ligand field term. The Hamiltonian of the static crystal field can involve the terms of all orders, which are invariant under the local group of the average geometry of the complex. In the laboratory frame, the random rotation of the complex is the only source of modulation of this Hamiltonian, whereas an additional Ornstein–Uhlenbeck process is needed to describe the time fluctuations of the Hamiltonian of the transient crystal field. A numerical procedure for computing the electronic paramagnetic resonance (EPR) spectra is proposed and discussed. For the $[{\mathrm{Gd(H}}_{\mathrm{2}}{\mathrm{O)}}_8{]}^{\text{3+}}$ octa-aqua ion and the $[{\mathrm{Gd(DOTA)(H}}_{\mathrm{2}}\mathrm{O)}{]}^{-}$ complex [$\mathrm{DOTA}\text{=1,4,7,10}$ -tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclo dodecane] in water, the predictions of the Redfield relaxation theory are compared with those of the Monte Carlo approach. The Redfield approximation is shown to be accurate for all temperatures and for electronic resonance frequencies at and above X-band, justifying the previous interpretations of EPR spectra. At lower frequencies the transverse and longitudinal relaxation functions derived from the Redfield approximation display significantly faster decays than the corresponding simulated functions. The practical interest of this simulation approach is underlined.