The synthesis of dinuclear molecular complexes [Eu2(dbm)6(bipyMO)2], 1, [Tb2(dbm)6(bipyMO)2], 2, [Eu2(tta)6(bipyMO)2], 3 [Eu2(hfac)6(bipyMO)3], 4, [Tb2(hfac)6(bipyMO)3], 5 is here reported (bipyMO = 4,4′‐bipyridine N‐oxide, Hdbm = dibenzoylmethane, Htta = thenoyltrifluoroacetone, Hhfac = hexafluoroacetylacetone). The products were obtained in mild conditions and with high yields reacting anhydrous lanthanide β‐diketonates and bipyMO in 1:1 or 1.5 molar ratio in toluene. X‐ray single crystal studies on 2, 3, 4 showed that the heterotopic ligands are hypodentate, bridging the two lanthanide centres exclusively through the oxygen atom. Photoluminescence studies show bright red emissions from europium derivatives with absolute quantum yields up to 44 %.

The tetratopic ligands 1,4-bis(2-ethylbutoxy)-2,5-bis(3,2’:6’,3’’-terpyridin-4’-yl)benzene (1) and 1,4-bis(3-methylbutoxy)-2,5-bis(3,2’:6’,3’’-terpyridin-4’-yl)benzene (2) have been prepared and characterized by 1H and 13C{1H} NMR, IR, and absorption spectroscopies and mass spectrometry. Reactions of 1 and 2 with cobalt(II) thiocyanate under conditions of crystal growth at room temperature result in the formation of [{Co(1)(NCS)2}·MeOH·3CHCl3]n and [{Co(2)(NCS)2}·0.8MeOH·1.8CHCl3]n. Single-crystal X-ray diffraction reveals that each crystal lattice consists of a trinodal self-penetrating (62.84)(64.82)(65.8)2 net. The nodes are defined by two independent cobalt centres and the centroids of two crystallographically independent ligands which are topologically equivalent.

Five coordination polymers formed from combinations of copper(II) acetate and 4′-(4-alkyloxyphenyl)-3,2′:6′,3″-terpyridines with methoxy (1), n-butoxy (2), n-pentyloxy (3) and n-heptyloxy (4) substituents are reported. Reaction of 1 with Cu(OAc)2∙H2O leads to the 1D-polymer [Cu2(μ-OAc)4(1)]n in which {Cu2(μ-OAc)4} paddle-wheel units are connected by ligands 1, or [{Cu4(μ3-OH)2(μ-OAc)2(μ3-OAc)2(AcO-κO)2(1)2}·2MeOH]n in which centrosymmetric tetranuclear clusters link pairs of ligands 1 to give a double-stranded 1D-polymer. Layering solutions of Cu(OAc)2∙H2O (in MeOH) over 2, 3 or 4 (in CHCl3) leads to the assembly of the 1D-polymers [2{Cu2(μ-OAc)4(2)}·1.25MeOH]n, [Cu2(μ-OAc)4(3)]n and [{Cu2(μ-OAc)4(4)}·0.2CHCl3]n. In all compounds, the 3,2′:6′,3″-tpy unit coordinates only through the outer pyridine rings, but the conformation of the 3,2′:6′,3″-tpy responds to changes in the length of the alkyloxy tails leading to changes in the conformation of the polymer backbone and in the packing of the chains in the crystal lattice in the chains featuring {Cu2(μ-OAc)4} paddle-wheel linkers.

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The consistent assembly of a (65.8) cds net is observed in reactions of cobalt(II) thiocyanate with 1,4-bis(n-alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene ligands in which the n-alkyloxy substituents are n-propyl (ligand 3), n-butyl (4), n-pentyl (5), n-hexyl (6), n-heptyl (7), and n-octyl (8). Crystals were grown by layering a methanol solution of Co(NCS)2 over a 1,2-dichlorobenzene solution of each ligand. The choice of crystallization solvents is critical in directing the assembly of the cds net. Single-crystal structures of [Co(NCS)2(3)]n.3.5nC6H4Cl2, [Co(NCS)2(4)]n.5.5nC6H4Cl2, [Co(NCS)2(5)]n.4nC6H4Cl2, [Co(NCS)2(6)]n.3.8nC6H4Cl2, [Co(NCS)2(7)]n.3.1nC6H4Cl2, and [Co(NCS)2(8)]n.1.6nC6H4Cl2.2nMeOH (C6H4Cl2 = 1,2-dichlorobenzene) are presented and compared. The n-alkyloxy chains exhibit close to extended conformations and are accommodated in cavities in the lattice without perturbation of the coordination framework.