1 research outputs found
Single Crystal EPR of the Mixed-Ligand Complex of Copper(II) with lāGlutamic Acid and 1,10-Phenanthroline: A Study on the Narrowing of the Hyperfine Structure by Exchange
We report an EPR study at X- and Q-bands of polycrystalline
and
single crystal samples of the mixed copperĀ(II) complex with l-glutamic acid (glu) and 1,10-phenantroline (phen), [CuĀ(glu)Ā(phen)Ā(H<sub>2</sub>O)]<sup>+</sup> NO<sub>3</sub><sup>ā</sup>Ā·2Ā(H<sub>2</sub>O). The polycrystalline sample spectrum at Q-band showed well
resolved <i>g</i><sub>ā„Ā </sub>and <i>g</i><sub>ā„</sub> features and partially solved hyperfine structure
at <i>g</i><sub>ā„</sub>, typical for weakly exchange
coupled systems. This is confirmed from the angular variation of the
EPR spectra which shows for certain magnetic field orientations a
partially solved hyperfine structure characteristic of weak exchange,
whereas a single Lorentzian line corresponding to strong exchange
is observed for others. Analysis and simulation of the single crystal
EPR spectra were performed using the random frequency modulation model
of Anderson. Numerical simulations of the angular variation of the
EPR spectra showed that the narrowing of the hyperfine structure is
due to an exchange-mediated mechanism in which transitions between
any pair of lines are equally likely. The exchange interaction responsible
for this process is mediated by hydrophobic interactions between two
phen molecules and a mixed chemical path of the type CuAāO<sub>ap</sub>HĀ·Ā·Ā·OāCāO<sub>eq</sub>āCuB,
for which we evaluated an average isotropic exchange parameter |<i>J</i>| ā 25 Ć 10<sup>ā4</sup> cm<sup>ā1</sup>