The quantum nature of single-ion magnets, single-molecule magnets, and single-chain magnets has been manifested among other phenomena by magnetic hysteresis due to slow spin relaxation, competing with fast quantum tunneling at low temperatures. Slow spin relaxation, described by Arrhenius-type law with the effective barrier energies Ueff = 50 cm–1, was discovered 3 decades ago in paramagnetic Mn12-acetate complex of oxy-bridged mixed-valence manganese ions, below the blocking temperature TB = 3 K. In contrast to common magnetic materials, it is governed primarily by magnetic anisotropy, set by zero-splitting of spin states of a magnetic ion in a field of ligands, and spin-lattice coupling. The emerging studies on the border of coordination chemistry, physics of spin systems with reduced dimensionality, and nanotechnologies, were performed in search of routes for enhancement of Ueff and TB characteristics, in line with increase of operation temperature and quantum correlation time, mandatory for quantum applications. The best results with TB ∼ 80 K and Ueff ∼ 1261 cm–1, were obtained for DyIII single-ion magnet, so far. Numerous excellent research and review articles address particular activities behind this achievement. It follows, that present challenges are dictated by the rational development of novel, smart magnetic molecules, featured by butterfly cores, cyano-bridges, 2D metal-organic frameworks, and metal-free graphene nanoclusters, as well as stable free radicals, magnetized by spare electrons. These species are briefly considered here with respect to the unique experience of international collaborative activity, established by Prof. Juan Bartolomé.