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Abstract: The reaction of chiral sodium complexes, 1∞[Na(S‐valmetH)]⋅H2O (1‐S) and 1∞[Na(R‐valmetH)]⋅H2O (1‐R), with copper(II) acetate affords chiral one‐dimensional coordination polymers with the formulas 1∞[Cu(S‐valmet)(H2O)]⋅H2O (2‐S) and 1∞[Cu(R‐valmet)(H2O)]⋅H2O (2‐R) (R/S‐valmetH2 are Schiff base proligands resulting from the condensation reactions between o‐vanillin and R/S‐methionine). The copper ions are connected by the carboxylato groups belonging to the amino‐acid moieties, resulting in infinite chains showing syn‐anti out‐of‐plane bridging mode. The circular dichroism spectra of 1‐S, 1‐R, 2‐S, and 2‐R confirm their enantiomeric nature. Compounds 2‐S and 2‐R undergo a two‐step single‐crystal‐to‐single‐crystal transformation, with the elimination of the lattice and coordinated water molecules: 1∞[Cu(S‐valmet)(H2O)]⋅H2O (2‐S)→1∞[Cu(S‐valmet)]⋅H2O (3‐S⋅H2O)→1∞[Cu(S‐valmet)] (3‐S) and 1∞[Cu(R‐valmet)(H2O)]⋅H2O (2‐R)→1∞[Cu(R‐valmet)]⋅H2O (3‐R⋅H2O)→1∞[Cu(R‐valmet)] (3‐R), respectively. During these transformations, every pair of face‐to‐face chains present in 2‐S (or 2‐R) has been “zipped up” into a chiral double chain through the removal of the aqua ligands and their replacement by the carboxylato oxygen atoms from the neighboring chain. Consequently, each carboxylato group now bridges three copper ions. The conversion of the single chains, 2‐S and 2‐R, into the double chains, 3‐S and 3‐R, is accompanied by a change of the strength of the exchange interactions between the copper ions: weak antiferromagnetic couplings are observed in compound 2‐S (J/kB=−1.23(5) K, H=−2J ΣSiSi+1) and relatively strong in compound 3‐S (J/kB=−76.0(8) K). When the racemic mixture of the ligands, R,S‐valmetH2, is employed, in the same experimental conditions, a racemic mixture of mononuclear compounds, [Cu(R,S‐valmet)(H2O)2]⋅H2O (4‐RS), is obtained. Compound 4‐RS also undergoes a SCSC transformation with the elimination of the lattice and one of the coordinated water molecules, resulting in a racemic mixture of chiral chains, 1∞[Cu(R‐valmet)(H2O)]⋅1∞[Cu(S‐valmet)(H2O)] (5‐RS). In this compound, the coupling of the copper(II) ions within the chains is weak and ferromagnetic (J/kB=+0.10(2) K). These results prove that the chirality of the valmetH2 ligands (optically pure or racemic mixture) plays a key role in the self‐assembly process of the copper(II) complexes. [ABSTRACT FROM AUTHOR]