Explorer Structural , Magnetic , and Electronic Properties of Phenolic Oxime Complexes of Cu and

General rights Copyright for the publications made accessible via the Edinburgh Research Explorer is retained by the author(s) and / or other copyright owners and it is a condition of accessing these publications that users recognise and abide by the legal requirements associated with these rights. Take down policy The University of Edinburgh has made every reasonable effort to ensure that Edinburgh Research Explorer content complies with UK legislation. If you believe that the public display of this file breaches copyright please contact [email protected] providing details, and we will remove access to the work immediately and investigate your claim. We thank the EPSRC and the Japanese Science and Technology agency (JST) for funding. This work has made use of the resources provided by the EaStChem Research Computing Facility Synopsis: Phenolic oxime complexes of Ni(II) and Cu(II) show planar structures with intermolecular interactions controlled by the steric bulk of peripheral alkyl groups to give either isolated molecules or π-stacked structures. Both Cu and Ni complexes show limited orbital interaction between the metal and ligands, although greater for Ni than Cu. The Cu complexes show antiferromagnetic chain behaviour and weaker intermolecular interactions than the Ni complexes in the solid state or in a thin film. Abstract Square planar complexes of the type Ni(L 1) 2 , Ni(L 2) 2 , Cu(L 1) 2 and Cu(L 2) 2 where L 1 H = 2-hydroxy-5-t-octylacetophenone oxime and L 2 H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterised by single-crystal X-ray diffraction, cyclic voltammetry, UV/Vis spectroscopy, field-effect-transistor measurements, DFT/TDDFT calculations and in the case of the paramagnetic species, EPR and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L 1) 2 contrasting with π-stacking interactions for M(L 2) 2 (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L 2) 2 but ideal paramagnetic behaviour for Cu(L 1) 2 down to 1.8 K. Despite isostructural single crystal structures for M(L 2) 2 , thin-film X-ray diffraction and SEM revealed different morphologies depending on the metal and the deposition method (vapour or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalised ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/Vis spectroscopy. The complexes M(L 2) 2 showed poor charge transport in an FET …