We report a rapid and facile route to the synthesis of a family of MnIII monomers of general formula [MnIIIF3(H2O)(L1–6)]·xH2O·yMeOH [L1 = 2,2′-bipyridyl, x = 2, y = 0 (1′); L2 = 1,10′-phenanthroline, x = y = 0 (2′); L3 = 6-methyl-2,2′-dipyridyl, x = y = 0 (3), L4 = 4,4-dimethyl-2,2′-dipyridyl, x = 2, y = 0 (4), L5 = 5,5′-dimethyl-2,2′-dipyridyl, x = 0, y = 0.5 (5); L6 = 5-chloro-1,10-phenanthroline, x = y = 0 (6)]. Magnetic susceptibility and magnetisation experiments have been employed to elucidate the D tensor for each family member (ranging from –3.01 cm–1 in 2′ to –4.02 cm–1 in 5), while multi-frequency/high-field EPR spectroscopic measurements and subsequent simulations gave similar values for complexes 1′ (–4.25 cm–1), 2′ (–4.03 cm–1), 4 (–3.90 cm–1) and 5 (–4.04 cm–1). The terminal Mn–F vibrational stretches in 1′–6 have been probed using Raman spectroscopy.