Supramolecular structure of N,N-bis(2-hydroxybenzyl)alkylamine:: From hydrogen bond assembly to coordination network in guest acceptance

N,N-BiS(2-hydroxybenzyl)alkylamine (HBA) was described as a model to simplify the supramolecular system of polybenzoxazines. The single crystal X-ray analysis revealed that HBA forms a dimeric assembly based on its simultaneous inter- and intramolecular hydrogen bond network. When the HBA accepted the copper ion, the dimeric assembly HBA changed its primary hydrogen bond network to charge transfer coordination as clarified by the single crystal analysis as well as the superimposed structure based on DMol(3) calculation. The supramolecular structure of HBA and copper also exhibited the role of solvent molecules in the packing structure which is a rare example showing the host accepts not only the metal ions but also the neutral molecules in the same time. The cyclization of HBA with esters or ethers to macrocyclic compounds was also an important model reaction to show how the backbone molecules self-stabilized with the hydrogen bond network initiate the simple, effective and efficient macrocyclic reaction.