Coordination-driven self-assemblies of two hetero-trinuclear [Cu(II)2Ln(III)] (Ln = La and Ce) complexes with a flexible bis(salamo)-type ligand

d-Block transition metal(II)-lanthanide(III) (3d-4f) hetero-trinuclear [Cu(II)(2)Ln(III)] (Ln = La and Ce) complexes [Cu2La(L)(n(2)-NO3)(3)(CH3OH)(2)]center dot 2CH(3)OH (1) and [Cu2Ce(L)(n(2)-NO3)(3)(CH3OH)(2)]center dot 2CH(3)OH (2) are described, both of which are formed by a flexible symmetrical bis(salamo)-type ligand H4L. The two 3d-4f complexes have been synthesized and characterized by elemental analyses, IR spectra and UV-Vis spectroscopy. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction analyses. In 1 and 2, each Cu(II) ion (Cu1 or Cu2) is located in the N2O2 cavity of an (L)(4-) unit, while the apex is occupied by one oxygen atom of the coordinated methanol molecule, forming a penta-coordinated square pyramidal geometry. The lanthanide(III) (La or Ce) ion is located in the O-6-donor coordination sphere of the completely deprotonated (L)(4-) unit and coordinated with the other six oxygen atoms of the three nitrate ligands to form a twelve-coordinated icosahedron. At the same time, the supramolecular structures are formed by intermolecular hydrogen bonding interactions and quantitatively determined by Hirshfeld surfaces analyses. Fluorescence properties and DFT calculations of 1 and 2 were also studied.