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Charge-neutral hexadecanuclear nanoclusters [Co16(OH)4(ib)20(thme)2(Hthme)2(H2O)6]·MeCN·4H2O (1) and [Co16(OH)4(ib)20(thmp)2(Hthmp)2(H2O)6]·MeCN·4H2O (2) have been prepared from the reaction of Co(II) isobutyrate (Co(ib)2) with 1,1,1-tris(hydroxymethyl)ethane (H3thme) or 1,1,1-tris(hydroxymethyl)propane (H3thmp) and comprehensively characterized. Single-crystal X-ray diffraction reveals that the common mixed-valent centrosymmetric {Co(II)14Co(III)2} core of 1 and 2 represents an unprecedented arrangement of two planar {Co7} disk-like fragments with a central Co(III) ion surrounded by six Co(II) ions connected by two additional Co(II) ions. The two {Co7} fragments are non-coplanar and lie in parallel planes separated by a distance of 2.772 Å, with two additional Co(II) centers between these planes. Hirshfeld surface (HS) analysis was used to gain additional insight into the interactions responsible for the packing of nanoclusters in the title compounds. Magnetic characterization of 1 revealed that the 14 Co(II) centers exhibit predominantly ferromagnetic exchange interactions, but some antiferromagnetic exchange pathways are also present. [ABSTRACT FROM AUTHOR]

Charge-neutral [Na2Fe10O6(OH)4(isobutyrate)14(MeO)2(MeCN)2] coordination clusters, comprising a hollow 'Chinese lantern'-like shell of six condensed planar triangular {FeIII3(μ3-O)} motifs, form upon ultrasonication of trinuclear Fe(III) isobutyrate units in acetonitrile in the presence of sodium azide and 4,4′-bipyridine (bpy), resulting in {[Na2Fe10O6(OH)4(isobutyrate)14(bpy)(MeO)2(MeCN)2]·MeOH}n in which the dodecanuclear cluster units are bpy-bridged into 1D chains. [ABSTRACT FROM AUTHOR]

A series of compounds containing the d-block unit [[Os(phen)[(CN).sub.4]].sup.2-] in combination with various near-infrared-emissive Ln(III) cations are reported. The results from the measurement of the energy transfer rates for Yb(III), Er(III), Nd(III), and Pr(III) provide insight into energy-accepting f-f states of the different Ln(III) ions.

The structural and photophysical properties of various polynuclear assemblies obtained from [[Os(bipy)[(CN).sub.4]].sup.2-] and its relatives are discussed. The results show that the lifetime of these complexes can be increased by the binding of metal cations to cyanides.

Two families of charge‐neutral heterometallic Fe‐4f coordination compounds comprising isobutyrate and amino alcoholate linkers were found to form exclusively upon ultrasonication irradiation. Under one‐pot conditions, the trinuclear precursor [Fe3O(O2CCHMe2)6(H2O)3](NO3)·2(MeCN)·2(H2O) reacts with Ln(NO3)3·xH2O or Y(NO3)3·6H2O, N‐butyldiethanolamine (bdeaH2) and NaN3 in methanol to yield the decanuclear clusters [Fe6M4(O2CCHMe2)8(N3)2(bdea)10]·n(solvent) (MIII = Y (1a·3MeOH), Gd (2a·2.5MeOH), Dy (3a·3.5MeOH·0.5H2O), Tb (4a·2MeOH), Ho (5a·2MeOH), as well as subsequently the hexanuclear compounds [Fe4M2(OH)2(O2CCHMe2)6(N3)2(bdea)4]·2(solvent) (MIII = Y (1b·2MeOH), Gd (2b·2MeOH), Dy (3b·2MeOH, 3c·2EtOH), Tb (4b·2MeOH), Er (6b·2MeOH), Tm (7b·2MeOH)). The {Fe6M4} clusters feature a wheel‐shaped architecture with the metal ions, interlinked by carboxylate and polyalcoholamine bridges, forming a saddle‐like ring. The hexanuclear {Fe4M2} clusters comprise two {Fe2M} triangles, connected via two bridging µ3‐OH– groups, which form a condensed core of metals additionally linked by deprotonated tripodal bdeaH2 ligands and bridging carboxylates. Magnetic measurements revealed predominant strong antiferromagnetic interactions within compounds 1–7 and out‐of‐phase signals for {Fe6Dy4} (3a·3.5MeOH·0.5H2O), {Fe6Tb4} (4a·2MeOH), and {Fe4Dy2} (3b·2MeOH). [ABSTRACT FROM AUTHOR]