although the Co(hmba)3[Co(SCN)4] crystal features a 3D rather than a 2D network. This clearly confirms the universality of the effect. However, in the remaining part of this article, we focus on the Co(hmba)3[CoBr4] system as it features the best glass-forming ability and thus serves as a good model system for understanding the mechanism of the water interaction with the hybrid network. sugars, organic polymers, and silicate glasses as obtained from Refs. .