Oligonuclear 3d–4f Complexes as Tectons in Designing Supramolecular Solid‐State Architectures: Impact of the Nature of Linkers on the Structural Diversity

Heteronuclear cationic complexes, [LCuLn] 3+ and [(LCu) 2 Ln] 3+ , were employed as nodes in designing high‐nuclearity complexes and coordination polymers with a rich variety of network topologies (L is the dianion of the Schiff base resulting from the 2:1 condensation of 3‐methoxysalycilaldehyde with 1,3‐propanediamine). Two families of linkers have been chosen: the first consists of exo ‐dentate ligands bearing nitrogen‐donor atoms (bipyridine (bipy), dicyanamido (dca)), whereas the second consists of exo ‐dentate ligands with oxygen‐donor atoms (anions derived from the acetylenedicarboxylic (H 2 acdca), fumaric (H 2 fum), trimesic (H 3 trim), and oxalic (H 2 ox) acids). The ligands belonging to the first family prefer copper( II ) ions, whereas the ligands from the second family interact preferentially with oxophilic rare‐earth cations. The following complexes have been obtained and crystallographically characterized: [LCu II (OH 2 )Gd III (NO 3 ) 3 ] ( 1 ), [{LCu II Gd III (NO 3 ) 3 } 2 (μ‐4,4′‐bipy)] ( 2 ), ${{{1\hfill \atop \infty \hfill}}}$ [LCu II Gd III (acdca) 1.5 (H 2 O) 2 ] ⋅ 13 H 2 O ( 3 ), ${{{2\hfill \atop \infty \hfill}}}$ [LCu II Gd III (fum) 1.5 (H 2 O) 2 ] ⋅ 4 H 2 O ⋅ C 2 H 5 OH ( 4 ), ${{{1\hfill \atop \infty \hfill}}}$ [LCu II Sm III (H 2 O)(Hfum)(fum)] ( 5 ), ${{{1\hfill \atop \infty \hfill}}}$ [LCu II Er III (H 2 O) 2 (fum)]NO 3 ⋅ 3 H 2 O ( 6 ), ${{{2\hfill \atop \infty \hfill}}}$ [LCu II Sm III (fum) 1.5 (H 2 O) 2 ] ⋅ 4 H 2 O ⋅ C 2 H 5 OH ( 7 ), [{(LCu II ) 2 Sm III } 2 fum 2 ](OH) 2 ( 8 ), ${{{1\hfill \atop \infty \hfill}}}$ [LCu II Gd III (trim)(H 2 O) 2 ] ⋅ H 2 O ( 9 ), ${{{2\hfill \atop \infty \hfill}}}$ [{(LCu II ) 2 Pr III }(C 2 O 4 ) 0.5 (dca)]dca ⋅ 2 H 2 O ( 10 ), [LCu II Gd III (ox)(H 2 O) 3 ][Cr III (2,2′‐bipy)(ox) 2 ] ⋅ 9 H 2 O ( 11 ), and [LCuGd(H 2 O) 4 {Cr(CN) 6 }] ⋅ 3 H 2 O ( 12 ). Compound 1 is representative of the whole family of binuclear Cu II –Ln III complexes which have been used as precursors in constructing heteropolymetallic complexes. The rich variety of the resulting structures is due to several factors: 1) the nature of the donor atoms of the linkers, 2) the preference of the copper( II ) ion for nitrogen atoms, 3) the oxophilicity of the lanthanides, 4) the degree of deprotonation of the polycarboxylic acids, 5) the various connectivity modes exhibited by the carboxylato groups, and 6) the stoichiometry of the final products, that is, the Cu II /Ln III /linker molar ratio. A unique cluster formed by 24 water molecules was found in crystal 11 . In compounds 2 , 3 , 4 , 9 , and 11 the Cu II –Gd III exchange interaction was found to be ferromagnetic, with J values in the range of 3.53–8.96 cm −1 . Compound 12 represents a new example of a polynuclear complex containing three different paramagnetic ions. The intranode Cu II –Gd III ferromagnetic interaction is overwhelmed by the antiferromagnetic interactions occurring between the cyanobridged Gd III and Cr III ions.