Figure 1. (top) Line drawing and labeled ORTEP plot of HbimDTDA (100 K; thermal ellipsoids at 50%); (bottom) singly occupied molecular orbital (SOMO) and electrostatic potential (ESP) surface calculated at uB3LYP/6-31G(d,p). Communication pubs.acs.org/JACS
A versatile synthetic methodology to access the first family of chiral verdazyl N,N'-chelate ligands is described and exemplified by N,N'-dimethyl-, N,N'-di-isopropyl-and N,N'-diphenyl oxoverdazyls bearing two isomers of the pinene-pyridine functional group. Their physical properties were probed by X-band EPR spectroscopy, cyclic voltammetry and DFT calculations. Preliminary reactivity studies show they can act as N,N'-chelate ligands affording a chiral 1 : 1 complex (3b) with CuCl 2 , which was characterized by single-crystal X-ray diffraction. Variable temperature EPR studies on (3b) confirm the presence of antiferromagnetic interactions between the spins of the Cu(II) ion and the verdazyl radical.The unique properties associated with chiral molecules and their interaction with light inter alia has a rich history that today plays a central role in many areas of chemistry that include organometallic, coordination compounds, metal nanoparticles and molecule-based materials.1 The marriage of chirality with free radical chemistry has also found applications in diverse fields ranging from enantioselective catalysis 2 to the development of chiral radicals as building blocks for chiral organic, or hybrid organic/inorganic magnets. 3 In the latter case, crystallization of chiral molecules into non-centrosymmetric space groups can confer unique physical phenomena that include ferroelectric, piezoelectric, second harmonic generation (SHG) and/or non-linear optical (NLO) properties. 4 Furthermore, in select examples, when magnetic chirality coexists with nuclear chirality, the spatial and temporal symmetry is simultaneously broken affording a range of magneto-optical properties that includes magneto-chiral dichroism (MChD).5
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