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Synthesis of new organo-lanthanide polyphosphides with an aromatic cyclo-[P4]2− moiety and a cyclo-[P3]3− moiety is presented.

A dinuclear dysprosium(iii) complex [Dy2(NO3)3(L)3]·nCH3OH (n = 1.20; HL = (2-[(2-hydroxy-propylimino)methyl]phenol)) (1) was isolated when dysprosium nitrate reacted with a solution of salicylaldehyde and 1-amino-2-propanol in a basic medium under in-situ reaction conditions.

The triangulo-{Er3} complex [Er3Cl(o-van)3(OH)2(H2O)5]Cl3·nH2O (n = 9.4; H(o-van) = o-vanillin) (1) was generated by an in situ method.

Herein, we present the synthesis and characterization of heteroleptic lanthanide complexes bearing a dianionic ��5-plumbole ligand in their coordination sphere. The reaction proceeds via a salt elimination reaction between the dilithioplumbole ([Li(thf)]$_2$[1,4-bis-tert-butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl] = [Li$_2$(thf)$_2$(��$^5$-L$^Pb$)]) and specifically designed [Ln(��$^8$-COT$^TIPS$)BH$_4$] precursors (Ln = lanthanide, La, Ce, Sm, Er; COT$^TIPS$ = 1,4-bis-triisopropylsilyl-cyclooctatetraenyl), that are capable of stabilizing a planar plumbole moiety in the coordination sphere of different trivalent lanthanide ions. In-depth ab initio calculations show that the aromaticity of the dianionic plumbole is retained upon coordination. Electron delocalization occurs from the plumbole HOMO to an orbital of mainly d-character at the lanthanide ion. The magnetic properties of the erbium congener were investigated in detail, leading to the observation of magnetic hysteresis up to 5 K (200 Oe s$^���1$), an unequivocal proof for single molecule magnet behavior in this system. The magnetic behavior of the erbium species can be modulated by manipulating the position of the lithium cation in the complex, which directly influences the bonding metrics in the central [(��$^5$-L$^Pb$)Er(��$^8$-COT$^TIPS$)]��� fragment. This allowed us to assess a fundamental magneto-structural correlation in an otherwise identical inner coordination sphere.

Amine groups are among the most effective systems for carbon dioxide capture. Reminiscent of the activation of nature's most abundant enzyme RuBisCO, the treatment of amines with CO2 in the presence of oxophilic metal ions, e.g. Mg2+, results in the formation of carbamates. Here we report the synthesis, structure and magnetic properties of three new dysprosium-carbamato complexes. The reaction of gaseous CO2 with N,N-diisopropylamine and DyCl3(DME)2 (DME = Dimethoxyethane) in toluene leads to the formation of the tetrametallic complex [Dy4(O2CNiPr2)10(O-C2H4–OMe)2]. The addition of 2-hydroxy-3-methoxybenzaldehyde-N-methylimine yields the hexametallic compound [Dy6(O2CNiPr2)8(O-C2H4–OMe)2(CO3)2(C9O2NH10)4] in which the metal sites form a chair-like configuration; The same hexanuclear motif is obtained using N,N-dibenzylamine. We show that by employing CO2 as a feedstock, we are able to capture up to 2.5 molecules of CO2 per Dy ion. Magnetic measurements show a decreasing χMT at low temperatures. Combining the experimental magnetic data with ab initio calculations reveils tilting of the easy axes and implies the presence of antiferromagnetic interactions between the Dy(III) metal ions.