A slow reaction between Nd3+ and piperazine-1,4-dicarbodithiolate disodium (Na-2(pipzdtc)) affords a three dimensional (3D) anionic [Nd(pipzdtc)(2)](n)(n-) framework with a dia net. The encapsulated disordered guest molecules could be partially exchanged by Ni2+ accompanied by the quenching of the typical NIR luminescence of Nd3+ ions
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