Cycloheptatrienyl-Bridged Triple-Decker Complexes.

The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, C7H73-) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements YIII and ErIII with a bridging cycloheptatrienyl ligand of the type [(thf)(BH4)2LnIII(µ-η7:η7-Cht)LnIII(BH4)(thf)2] is described first. The subsequent introduction of the CotTIPS ligand (CotTIPS = 1,4-(iPr3Si)2C8H62-) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)3K{(η8-CotTIPS)LnIII}2(µ-η7:η7-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck. These compounds are also the first examples of rare earth triple-decker complexes not bridged by a Cot derivative, based on purely carbon-based ligands. The magnetic properties of the respective ErIII congeners were investigated in detail, leading to the observation of antiferromagnetic coupling of the ErIII cations and a blocking temperature of 13.5 K. The conversion of the YIII compound [(thf)3K{(η8-CotTIPS)YIII}2(µ-η7:η7-Cht)] with [YIII(Cot)I(thf)2] resulted in ligand rearrangement and the selective formation of the first triple-decker complex ([(η8-CotTIPSYIII)2(µ-η8:η8-Cot)]) featuring two Cot ligands with different substituents in its coordination sphere.

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics.

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] (CotTIPS=1,4-(iPr3Si)2C8H6) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Y, Dy, Er). These compounds form Lewis-base-free one-dimensional coordination polymers when crystallised from toluene. In contrast, reaction of [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] in a 1 : 2 ratio led to the formation of heteroleptic triple-decker complexes [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Y, Dy, Er). Notably, these are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first trivalent lanthanide triple-decker featuring a heterocycle in the coordination sphere. Magnetic investigations reveal that [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Dy, Er) and [(η8-CotTIPS)ErIII(µ-η6:η6-DEDBA)ErIII(η8-CotTIPS)] exhibit Single-Molecule Magnet (SMM) behaviour. In the case of [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Dy, Er), the introduction of a second near lanthanide ion results in strong antiferromagnetic interactions, allowing the enhancement of the magnetic characteristic of the system, compared to the quasi isolated counterpart. This research renews the overlooked coordination chemistry of the DBA ligand and expands it to encompass rare-earth elements.

It's not just the size that matters: crystal engineering of lanthanide-based coordination polymers.

Synthesis and characterization of Lewis base free coordination polymers of selected lanthanides are presented. For this purpose, the substituted CotTIPS ligand (CotTIPS = 1,4-bis-triisopropylsilyl-cyclo-octatetraendiide) was used to synthesize homoleptic, anionic multidecker compounds of the type [K{LnIII(ɳ8-CotTIPS)2}]n. Depending on the solvent used for crystallization and the ionic radii of the lanthanide cations, three different categories of one-dimensional heterobimetallic coordination polymers were obtained in the solid state. For the early lanthanides La and Ce a unique helical conformation was obtained by crystallization from toluene, while the ionic radius of Pr seems to be a turning point towards the crystallization of zigzag polymers. For Er a third structural motif, a trapezoidal wave polymer was observed. Additionally, the zigzag polymer for all compounds could be obtained by changing the solvent from toluene to Et2O, reavealing a correlation between solid-state structure and ionic radii as well as solvent. While photoluminescence (PL) properties of Cot-lanthanide compounds are scarce, the La complexes show ligand centered green luminescence, whereas the Ce complexes reveal deep red emission origin from d-f transitions. The Er-compounds are single-molecule magnets, in which the magnetic relaxation of each Er ion occurs isolated from its neighbors at temperatures above 10 K, while below 9 K a strong antiferromagnetic coupling between the Er ions was seen.

Molecular cyclo-P3 complexes of the rare-earth elements via a one-pot reaction and selective reduction.

Synthesis of new organo-lanthanide polyphosphides with an aromatic cyclo-[P4]2- moiety and a cyclo-[P3]3- moiety is presented. For this purpose, the divalent LnII-complexes [(NON)LnII(thf)2] (Ln = Sm, Yb) ((NON)2- = 4,5-bis(2,6-diisopropylphenyl-amino)-2,7-di-tert-butyl-9,9-dimethylxanthene) and trivalent LnIII-complexes [(NON)LnIIIBH4(thf)2] (Ln = Y, Sm, Dy) were used as precursors in the reduction process of white phosphorus. While using [(NON)LnII(thf)2] as a one-electron reducing agent the formation of organo-lanthanide polyphosphides with a cyclo-[P4]2- Zintl anion was observed. For comparison, we investigated a multi-electron reduction of P4 by a one-pot reaction of [(NON)LnIIIBH4(thf)2] with elemental potassium. As products molecular polyphosphides with a cyclo-[P3]3- moiety were isolated. The same compound could also be obtained by reducing the cyclo-[P4]2- Zintl anion within the coordination sphere of SmIII in [{(NON)SmIII(thf)2}2(µ-η4:η4-P4)]. Reduction of a polyphosphide within the coordination sphere of a lanthanide complex is unprecedented. Additionally, the magnetic properties of the dinuclear DyIII-compound bearing a bridging cyclo-[P3]3- moiety were investigated.

Coinage Metal Bis(amidinate) Complexes as Building Blocks for Self-Assembled One-Dimensional Coordination Polymers.

The pyridyl functionalized amidinate [{PyC≡CC(NDipp)2 }Li(thf)2 ]n was used to synthesize a series of bis-amidinate complexes [{PyC≡CC(NDipp)2 }2 M2 ] (M=Cu, Ag, Au) with fully supported metallophilic interactions. These metalloligands were then used as building blocks for the synthesis of one-dimensional heterobimetallic coordination polymers using Zn(hfac)2 (hfac=hexaflouroacetylacetonate) for self-assembly. Interestingly, the three coordination polymers [{PyC≡CC(NDipp)2 }2 M2 ][Zn(hfac)2 ] (M=Cu, Ag, Au), exhibit a zig zag shape in the solid state. To achieve linear coordination geometry other connectors such as M'(acac) (M'=Ni, Co) (acac=acetylacetonate) were investigated. The thus obtained compounds [{PyC≡CC(NDipp)2 }2 Cu2 ][M'(acac)2 ] (M'=Ni, Co) are indeed linear heterobimetallic coordination polymers featuring a metalloligand backbone with fully supported metallophilic interactions.

Luminescent early-late-hetero-tetranuclear group IV - Au(I) bisamidinate complexes.

The versatile metalloligand [{HCCC(NDipp)2}2Au2] (dipp = 2,6-diisopropylphenyl) was converted into early-late heterotetrametallic complexes [{ClCp2MCCC(NDipp)2}2Au2] (M = Ti, Zr). These compounds show photoluminescence with either remarkably different (Ti) or similar (Zr) features as compared to related solely coinage metal containing acetylide amidinate complexes.