The crystal design of polar one-dimensional hydrogen-bonded copper coordination complexes

Dalton Transactions : an International Journal of Inorganic Chemistry
Kiyonori TakahashiTomoyuki Akutagawa

Abstract

Polar crystals exhibiting second-order harmonic generation (SHG) were designed by adjusting the intermolecular interactions of mononuclear Cu(ii) complexes in which one H2O, two pyridines (py), and two p-substituted benzoate (p-RBA) ligands (R = F, Cl, Br, I, CH3, and OCH3) were coordinated to a Cu(ii) ion, forming a penta-coordinated asymmetric [Cu(ii)(p-RBA)2(py)2(H2O)] mononuclear structure with a permanent dipole moment along the direction of the Cu-OH2 coordination axis. Each asymmetric [Cu(ii)(p-RBA)2(py)2(H2O)] complex formed a polar one-dimensional hydrogen-bonded chain, [Cu(ii)(p-RBA)2(py)2(H2O)]∞, between the non-coordinated carboxylate oxygen atom of the p-RBA ligand and the hydrogen atom of the H2O molecule. The formation of a polar crystal depended on the arrangement of polar hydrogen-bonded chains; the parallel arrangement of each polar chain resulted in a polar crystal. The chemical design of the R group in the p-RBA ligand enabled tuning of the magnitude of the interchain interactions and crystal polarity; polar crystals were obtained using p-RBA ligands with R = Cl, Br, I, and OCH3. In contrast, apolar crystals were grown from complexes containing p-RBA ligands with R = F and CH3. In all crystals, a polar two-d...Continue Reading

References

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