Magnetic, structural and computational studies on transition metal complexes of a neurotransmitter, histamine

► The study is one of very few EPR studies on histamine. ► Emphasize the role of histamine in supramolecular structure formation. ► Provides insight on structural behaviour of histamine which shows different conformational, tautomeric and ionic states. In this study, the transition metal complexes of histamine (His) prepared with oxalate (Ox), that is, [Cu(His)(Ox)(H 2O)], [Zn(His)(Ox)(H 2O)] (or [Zn(His)(Ox)]·(H 2O)), [Cd(His)(Ox)(H 2O) 2] and [Co(His)(Ox)(H 2O)], are investigated experimentally and computationally as part of ongoing studies on the mode of complexation, the tautomeric form and non-covalent interactions of histamine in supramolecular structures. The structural properties of prepared complexes are experimentally studied by X-ray diffraction (XRD) technique and Fourier transform infrared (FT-IR) spectroscopy and computationally by density functional theory (DFT). The magnetic properties of the complexes are investigated by electron paramagnetic resonance (EPR) technique. The [Cu(His)(Ox)(H 2O)] complex has a supramolecular structure constructed by two different non-covalent interactions as hydrogen bond and C–H⋯π interactions. EPR studies on [Cu(His)(Ox)(H 2O)], Cu 2+-doped [Zn(His)(Ox)(H 2O)] and [Cd(His)(Ox)(H 2O) 2] complexes show that the paramagnetic centers have axially symmetric g values. It is also found that the ground state of the unpaired electrons in the complexes is dominantly d x 2 - y 2 and unpaired electrons’ life time is spent over this orbital.