SHG-active Ln^III–[Mo^I(CN)₅(NO)]³⁻ (Ln = Gd, Eu) magnetic coordination chains: a new route towards non-centrosymmetric molecule-based magnets

The rare heteroligand pentacyanidonitrosylmolybdate(I) anion was employed in the construction of d–f bimetallic cyanido-bridged {[Ln^III(dmf)₆][Mo^I(CN)₅(NO)]} (Ln = Gd, 1; Eu, 2) chains crystallizing in the non-centrosymmetric Pna2₁ space group. 1 exhibits Gd–Mo antiferromagnetic coupling giving rise to the ferrimagnetic spin chain behaviour with the onset of magnetic ordering below 2 K, and shows high second harmonic generation (SHG) activity with SH susceptibility of 1.2 × 10⁻¹⁰ esu, opening a novel family of non-centrosymmetric molecule-based magnets.