Conformational Isomerism and Weak Molecular and Magnetic Interactions in Ternary Copper(II) Complexes of [Cu(AA)L‘]ClO₄·<i>n</i>H₂O, Where AA =<scp>l</scp>-Phenylalanine and<scp>l</scp>-Histidine, L‘ = 1,10-Phenanthroline and 2,2-Bipyridine, and<i>n</i>= 1 or 1.5:  Synthesis, Single-Crystal X-ray Structures, and Magnetic Resonance Investigations

Abstract

Weak molecular and magnetic exchange interactions in ternary copper(II) complexes, viz., [Cu(L-phe)(phen)(H(2)O)]ClO(4) (1), [Cu(L-phe)(bpy)(H(2)O)]ClO(4) (2), and [Cu(L-his)(bpy)]ClO(4).1.5H(2)O (3), where L-phe = L-phenylalanine, L-his = L-histidine, phen = 1,10-phenanthroline, and bpy = 2,2'-bipyridine, have been investigated. Single-crystal X-ray structures reveal that complex 2 crystallizes in a monoclinic space group P2(1), with unit cell parameters a = 7.422(7) A, b = 11.397(5) A, c = 12.610(2) A, beta = 102.10(5) degrees, V = 1043.0(11) A(3), Z = 2, R = 0.0574, and R(w) = 0.1657. Complex 3 crystallizes in a monoclinic space group C2, with a = 18.834(6) A, b = 10.563(4) A, c = 11.039(3) A, beta = 115.23(2) degrees, V = 1986.6(11) A(3), Z = 4, R = 0.0466, and R(w) = 0.1211. Molecules of 2, in the solid state, are self-assembled via weak intra- and intermolecular pi-pi stacking and H-bonding interactions. Molecules of 3 exhibit intermolecular dimeric association with the Cu.Cu separation being 3.811 A. X-ray structures and (1)H NMR studies reveal conformational isomerism in both solid and liquid states of complexes 1 and 2. The aromatic side chain of L-phe in 1 and 2 adopts either a "folded" (A) or an "extended" (B) conformation. Variable-temperature (1)H NMR and spin lattice relaxation measurements point out interconversion between conformations A and B at temperatures above 323 K. The change in molecular conformation induces a change in the electron density at the site of copper and band gap energy between HOMO and LUMO orbitals. Interestingly, in spite of paramagnetic nature, complexes 1 and 2 are amenable for both EPR and (1)H NMR spectroscopic studies. Single-crystal EPR spectra of 2 in three orthogonal planes are consistent with three-dimensional magnetic behavior. Intramolecular exchange dominates the dipolar interactions. The EPR spectra of 3 correspond to weak magnetic interactions between associated dimeric units. The structural and magnetic resonance investigations together reveal that the weak pi-pi stacking interactions are the electronic pathways for magnetic interactions in 1-3.