[Ln₁₆] complexes (Ln = Gd^III, Dy^III): molecular analogues of natural minerals such as hydrotalcite

Abstract

Two new hexadecanuclear lanthanide complexes employing the 1,5-bis(salicylidene)carbohydrazide (Hbsc) ligand are reported herein. These polynuclear aggregates crystallize in the R3[combining macron] space group, which is unprecedented in a family of lanthanide complexes with such high nuclearity. Magnetic susceptibility measurements reveal weak intramolecular interactions between the magnetic centres, and in the case of compound 2 (Dy), single-molecule magnet properties are observed.

Unravelling the Mechanism of CO2 Activation: Insights Into Metal‐Metal Cooperativity and Spin‐Orbit Coupling with {3d–4f} Catalysts

“…For Dy and Er, the Gd geometries were assumed as the lanthanides are known to yield analogues structures. [35,36,37] However, we have compared the bond lengths of the first coordination sphere of the X-ray structures of all three complexes where the average deviation of LnÀ O bond length is less than 0.01 Å, clearly suggesting that they these are structurally analogues as reported elsewhere (as shown in Figure S14). Single-point calculations are done for the Dy and Er complexes to compare the energies and reactivity of Dy, Gd and Er complexes.…”

Self-assembly of octanuclear Ln(iii)-based clusters: their large magnetocaloric effects and highly efficient conversion of CO2

“…The τ 0 value of 2 is consistent with the reported values of 10 −6 -10 −12 s for polynuclear or high-nuclear Dy(III)-based SMMs. [79][80][81][82][83][84][85][86][87][88][89][90][91] In addition, the Cole-Cole diagram of cluster 2 was plotted via χ″ vs. χ′ from 2.0 to 14.0 K under the optimum field (H dc = 3000…”

Metal–Organic Frameworks Based on Group 3 and 4 Metals

“…The reported Ln 3+ clusters mainly include trinuclear (Ln 3 , Ln = Gd, Tb, Dy, Ho), [16,17] tetranuclear (Ln 4 , Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), [18][19][20][21][22][23][24][25][26][27] pentanuclear (Ln 5 , Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), [25] hexanuclear (Ln 6 , Ln = Pr, Ce, Eu, Gd, Tb, Dy, Er and Y), [27][28][29][30] octagon (Ln 8 , Ln = Gd, Tb, Dy, Ho), [31] nine-nuclear (Ln 9 , Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho), [32][33][34] eleven-nuclear (Ln 11 , Ln = Gd, Tb, Dy), [35] dodecanuclear (Ln 12 , Ln = Eu, Gd, Tb, Dy), [32,[36][37][38] hexadecanuclear (Ln 16 , Ln = Gd, Dy) clusters. [39] The number of Ln nuclei in Ln 3+ clusters was often controlled by the preferred coordination geometry of ligands [32] and the reaction environments. [37] [195] Corrole-MOF-1 Zr 6 O 4 (OH) 7 (H 2 O) 3 (CO 2 ) 9 TCPC 3,9-c gfy 2545 [193] MOF-525 Zr 6 O 4 (OH) 4 (CO 2 ) 12 TCPP 4,12-c ftw 1936 [197,198] The largest An(IV)-oxo cluster reported is An 38 complexes including U 38 , [40,41] Pu 38 and Np 38 .…”