Nitrophenolate as a Building Block for Lanthanide Chains, Layers, and Clusters

Abstract

Potassium o-nitrophenolate (1) was reacted with various lanthanide trichlorides under different reaction conditions. By using the smaller lanthanides and working under rigorous exclusion of air, infinite chains of composition [(THF)4[K(o-O2N-C6H4-O)4Ln]4]n (Ln = Y (2a), Er (2b), Lu (2c)) were obtained. Using the same conditions but performing the crystallization under air, tetradecanuclear clusters of composition H18[Ln14(micro-eta2-o-O2N-C6H4-O)8(eta2-o-O2N-C6H4-O)16(micro4-O)2(micro3-O)16] (Ln = Dy (3a), Er (3b), Tm (3c), Yb (3d)) were isolated. Using larger center metals such as samarium, europium, and terbium and working under rigorous exclusion of air, infinite layers of composition [[K2(o-O2N-C6H4-O)5Tb]n] (4) and [[K2(o-O2N-C6H4-O)5Ln)]n] (Ln = Sm (5a), Eu (5b)) were obtained. In 4 the layers have a closer packing than those in compound 5. The closer packing is a result of the increased coordination number of the lanthanide metal and the potassium atoms. In contrast, the more open structures of 5 results in channels which are rectangular through the layers. All compounds reported including 1 have been investigated by single-crystal X-ray diffraction.

Rare‐Earth Metal Oxo/Hydroxo Clusters – Synthesis, Structures, and Applications

“…Schematic depiction of the pentanuclear square pyramidal unit, which can be regarded as a building block for nonanuclear and tetradecanuclear clusters. [37] Beside the usage of alkoxides as ligands, such pentanuclear cluster compounds with other ligands, such as dibenzoylmethane and functionalized versions of it, are also known. [10,[49][50][51][52][53][54][55] According to Evans et al, the reaction between europium metal and 2,6-diisopropylphenol in propan-2-ol leads to the formation of pentanuclear complex H 5 [Eu 5 O 5 (OC 6 H 3 iPr 2 -2,6) 6 -(NCCH 3 ) 8 ] after recrystallization from acetonitrile.…”

“…The first clusters synthesized in our group by this synthetic method were published in 2000: we used o-nitrophenolate as a ligand and reported on the systematic preparation of lanthanide-oxygen clusters through partial hydrolysis of water-sensitive reaction mixtures. [37,38] 16 ] (Ln = Dy, Er, Tm, Yb) as orange crystals (Scheme 1). [37,38] The isolated cluster compounds each feature a crystallographic D 4d symmetry, and their inorganic cores each consist of three corner-sharing Ln (Ln = Dy, Er, Tm, Yb) octahedra, with a corner missing from each of the two outer octahedra (Figure 1).…”

“…[37,38] 16 ] (Ln = Dy, Er, Tm, Yb) as orange crystals (Scheme 1). [37,38] The isolated cluster compounds each feature a crystallographic D 4d symmetry, and their inorganic cores each consist of three corner-sharing Ln (Ln = Dy, Er, Tm, Yb) octahedra, with a corner missing from each of the two outer octahedra (Figure 1). 24 (μ 4 -OH) 2 (μ 3 -OH) 16 ].…”

A Family of Enneanuclear Iron(II) Single‐Molecule Magnets

“…À bridging mode in 1 is rather rare, having only been observed in a few transition metal [21,22] and lanthanide-A C H T U N G T R E N N U N G (III) [23][24][25][26] complexes. Two such cases are the enneanuclear complex cations of [Sm 9 A C H T U N G T R E N N U N G (acac) 16 (OH) 10 ]A C H T U N G T R E N N U N G [Cr 2 (CO) 10 A C H T U N G T R E N N U N G (m-H)] [24] and [Tb 9 A C H T U N G T R E N N U N G (Hesa) 16 [25] the metal cores of which, consisting of two square Ln 4 bases flanking a central Ln atom, display striking structural resemblance to those of complexes 1-3.…”

Near IR luminescent rare earth 3,4,5,6-tetrafluoro-2-nitrophenoxide complexes: Synthesis, X-ray crystallography and spectroscopy

“…Potassium 2-nitrophenoxide is known to combine with lanthanide ions to give a range of chains, layers and clusters [14]. We now report the synthesis, structures and luminescence properties for the first metal complexes to be prepared using the orange-coloured salts of 3,4,5,6-tetrafluoro-2-nitrophenol (1), a compound which is easily made by hydrolysis of commercially available pentafluoronitrobenzene, following the literature procedure [15].…”