Experimental and Theoretical Evaluation of Four NLO‐Active Divalent Transition‐Metal Complexes Supported by an Enantiomerically Pure Tetradentate Schiff Base Ligand

Abstract

This paper reports on a series of five chiral Schiff base push‐pull compounds derived from enantiomerically pure (1R,2R)‐(−)‐1,2‐diaminocyclohexane. The NiII, CuII, ZnII and PdII complexes supported by a ferrocene‐containing unsymmetrically‐substituted N2O2 quadridentate Schiff base ligand were prepared via template reactions and isolated in 74–87 % yields. A combination of EA, IR, UV/vis and 1H/13C{1H} NMR spectroscopy, HRMS spectrometry, cyclic voltammetry and single‐crystal X‐ray analysis (for the proligand 2 and its NiII derivative 3), together with computational methods (DFT and TD‐DFT) was used to fully characterize and study the properties of all products. Both 2 and 3 crystallize in the orthorhombic non‐centrosymmetric space group P212121, with two (R,R)‐(−)‐chiral carbon atoms in their structure. Second‐order nonlinear polarizabilities β have been measured by using Harmonic Light Scattering at 1.91 μm, with the Pd(II) species showing the higher NLO response of 460×10−30 esu.

Spectroscopy, molecular structure, and electropolymerization of Ni(ii) and Cu(ii) complexes containing a thiophene-appending fluorinated Schiff base ligand

“…In both cases, the carbonyl carbon that appears as a quartet ( 2 J C-F = 33 Hz) is upfield shifted by about 10 ppm upon coordination to Ni(II). 53 The -CF 3 groups show up as singlets at δ F −72.77 and −73.35 ppm in the 19 F NMR spectra.…”