Lanthanide-mediated tuning of electronic and magnetic properties in heterotrimetallic cyclooctatetraenyl multidecker self-assemblies.

The synthesis of a novel family of homoleptic COT-based heterotrimetallic self-assemblies bearing the formula [LnKCa(COT)3(THF)3] (Ln(iii) = Gd, Tb, Dy, Ho, Er, Tm, and Yb) is reported followed by their X-ray crystallographic and magnetic characterization. All crystals conform to the monoclinic P21/c space group with a slight compression of the unit cell from 3396.4(2) Å3 to 3373.2(4) Å3 along the series. All complexes exhibit a triple-decker structure having the Ln(iii) and K(i) ions sandwiched by three COT2- ligands with an end-bound {Ca2+(THF)3} moiety to form a non-linear (153.5°) arrangement of three different metals. The COT2- ligands act in a η8-mode with respect to all metal centers. A detailed structural comparison of this unique set of heterotrimetallic complexes has revealed consistent trends along the series. From Gd to Yb, the Ln to ring-centroid distance decreases from 1.961(3) Å to 1.827(2) Å. In contrast, the separation of K(i) and Ca(ii) ions from the COT-centroid (2.443(3) and 1.914(3) Å, respectively) is not affected by the change of Ln(iii) ions. The magnetic property investigation of the [LnKCa(COT)3(THF)3] series (Ln(iii) = Gd, Tb, Dy, Ho, Er, and Tm) reveals that the Dy, Er, and Tm complexes display slow relaxation of their magnetization, in other words, single-molecule magnet (SMM) properties. This behaviour is dominated by thermally activated (Orbach-like) and quantum tunneling processes for [DyKCa(COT)3(THF)3] in contrast to [ErKCa(COT)3(THF)3], in which the thermally activated and Raman processes appear to be relevant. Details of the electronic structures and magnetic properties of these complexes are further clarified with the help of DFT and ab initio theoretical calculations.

Versatility of cyclooctatetraenyl ligands in rare earth metal complexes of the [M2(COT)3(THF)2] (M = Y and La) type.

Two new organometallic cyclooctatetraenyl complexes of the type [M2(COT)3(THF)2] (M = Y and La) have been prepared, using optimized synthetic procedures, and fully characterized by X-ray diffraction analysis, IR and 1H NMR spectroscopies. The structures can be represented as formed by the double-decker [M(COT)2]- anion with an asymmetrically bound cationic [M(COT)(THF)2]+ unit. The COT rings in the anionic sandwich are not equidistant from the metal with the M-COTcentroid distances measuring at 1.991(5) Šand 2.074(5) Šfor [Y(COT)2]-vs. 2.045(4) Šand 2.154(5) Šfor [La(COT)2]-. The sandwich fragments are η2-coordinated to the second metal center with the average M-C distances of 2.837(4) Šand 2.879(5) Šfor yttrium and lanthanum complexes, respectively. The M-COTcentroid distances in the cationic unit are 1.962(4) Šfor the former and 2.009(2) Šfor the latter.

The dinuclear scandium(III) cyclooctatetraenyl chloride complex di-µ-chlorido-bis[(η8-cyclooctatetraene)(tetrahydrofuran-κO)scandium(III)].

Only a few cyclooctatetraene dianion (COT) π-complexes of lanthanides have been crystallographically characterized. This first single-crystal X-ray diffraction characterization of a scandium(III) COT chloride complex, namely di-µ-chlorido-bis[(η8-cyclooctatetraene)(tetrahydrofuran-κO)scandium(III)], [Sc2(C8H8)2Cl2(C4H8O)2] or [Sc(COT)Cl(THF)]2 (THF is tetrahydrofuran), (1), reveals a dimeric molecular structure with symmetric chloride bridges [average Sc-Cl = 2.5972 (7) Å] and a η8-bound COT ligand. The COT ring is planar, with an average C-C bond length of 1.399 (3) Å. The Sc-C bond lengths range from 2.417 (2) to 2.438 (2) Š[average 2.427 (2) Å]. Direct comparison of (1) with the known lanthanide (Ln) analogues (La, Ce, Pr, Nd, and Sm) illustrates the effect of metal-ion (M) size on molecular structure. Overall, the M-Cl, M-O, and M-C bond lengths in (1) are the shortest in the series. In addition, only one THF molecule completes the coordination environment of the small ScIII ion, in contrast to the previously reported dinuclear Ln-COT-Cl complexes, which all have two bound THF molecules per metal atom.