A straightforward access is provided to iron(II) complexes showing exceedingly slow spin-state interconversion by utilizing trigonal-prismatic directing ligands (L-n) of the extended-tripod type. A detailed analysis of the interrelations between complex structure (X-ray diffraction, density functional theory) and electronic character (SQUID magnetometry, Mossbauer spectroscopy, UV/vis spectroscopy) of the iron(II) center in mononuclear complexes [FeLn] reveals spin crossover to occur along a coupled breathing/torsion reaction coordinate, shuttling the complex between the octahedral low-spin state and the trigonal-prismatic high-spin state along Bailar's trigonal twist pathway. We associate both the long spin-state lifetimes in the millisecond domain close to room temperature and the substantial barriers against thermal scrambling (E-a approximate to 33 kJ mol(-1), from Arrhenius analysis) with stereochemical constraints. In particular, the topology of the kappa N-6 ligands controls the temporary and structural dynamics during spin crossover.