Structural Diversity of Infinite 3d–4f Heterometallic Cluster Compounds Driven by Various Lanthanide Radii

Abstract

The syntheses, structures, and characterization of six Ln(3+)-Cu(2+)-glycine (Hgly) coordination polymers are described in this paper. They represent three types of structures. Type I (Ln=La (1), Pr (2), and Sm (3)) is a 1D catenarian polymer comprising [Ln(2)] nodes bridged by four cis-Cu(gly)(2) linkers. Type II (Ln=Eu (4) and Dy (5)) is a 2D open framework with a 4(4)-net, composed of novel [Ln(6)Cu(22)] cluster nodes linked by trans-Cu(gly)(2) linkers. Furthermore, the inner structures of the [Ln(6)Cu(22)] nodes, and the connection mode between the nodes and linkers are slightly different for 4 and 5. Type III (Ln=Er (6)) is a 3D open framework with a novel 3(6)4(18)5(3)6 topology, made up of [Er(6)Cu(24)] cluster nodes and trans-Cu(gly)(2) linkers. The rich variety of the resulting structures owes itself mainly to the interselection between the dynamic control of metalloligands and cationic components. A transition from frequency dependence to frequency independence is observed in the field-induced magnetization lag for 1-3. The frequency dependence at low temperatures may come from the antiferromagnetic Cu--Cu interaction through the [Ln(2)] nodes, whereas the frequency independence may be due to the disappearance of the antiferromagnetic Cu--Cu interaction at high temperatures.

A New 3D 4d‐4f La–Ag Coordination Polymer Constructed by Interesting [Ag2]n and Flat [La2(IN)6(CH3COO)]n Layers

“…The coordination model of La(2) displays a distorted bicapped trigonal‐prismatic arrangement, in which the atoms O(2) and O(14) are located at the capping positions. TheLa–O bond lengths range from 2.434(6) to 2.853(5) Å, whereas the O–La–O bond angles range from 60.35(15) to 149.22(19)°, which are similar to the values of other reported lanthanum compounds 18,19. It is noteworthy that the six IN – ligands (crystallographically independent) coordinated to lanthanum ions are different, which become obvious by the different coordination modes of the carboxyl groups.…”

“…As is known, lanthanide and transition metal ions have different affinities for O and N donors, the selection of appropriate ligands to chelate two kinds metal ions has provided an impressive variety of possible complexes. Thus, structurally well‐defined materials are rationally synthesized by self‐assembly processes by using the judiciously chosen ligands, such as pyridine‐carboxylate,7 iminodiacetic acid,8 and glycine 9. Nevertheless, the synthesis of 3d‐4f coordination polymers has become widespread in recent years, also the research interest on the exploration of heteronuclear 4d‐4f complexes, attributed to their potential usage as sensor or luminescent materials, has grown this time 10–12.…”

Hydrothermal synthesis, crystal structure and luminescence of two new 2D coordination polymers [Ln(IN)(CO3)(H2O)] (LnLa, Eu) constructed by interesting flat lanthanide carbonate layers

“…1, each lanthanum atom is nine-coordinated by O atoms from one terminal water molecule, four carboxylate groups and one IN − ligand. The La_O bond lengths range from 2.486(5) Å to 2.616(6) Å, while the O\La\O bond angles range from 50.33(17) to 147.63(5)°, which are comparable with those reported La compounds [19,20]. The lanthanum subnetwork consists of chains of edge-sharing LaO 9 polyhedra along b axis and chains of corner-sharing polyhedra along a axis (Fig.…”

Breaking the Gordian Knot in the Structural Chemistry of Polyoxometalates: Copper(II)–Oxo/Hydroxo Clusters

“…Furthermore, the group of Wu succeeded in the preparation of multidimensional inorganic‐organic hybrid structures: 1) 1D chains {[ClO 4 @La 6 Cu 12 (OH) 24 {Cu 2 (OH)(H 2 O) 4 (gly) 3 } 6 Cu 2 ] 21+ } n ; 2) 2D open frameworks {[ClO 4 @La 6 Cu 12 (OH) 24 {Cu 2 (OH)(H 2 O) 11/3 (gly) 10/3 } 6 Cu 3 ] 23+ } n (Ln=Er III , Eu III or Gd III ), and [ClO 4 @Ln 6 Cu 12 (OH) 24 {Cu 2 (OH) 2/3 (Hgly) 2/3 (gly) 3 (H 2 O) 3 } 6 Cu] 25+ (Ln=Eu III or Dy III ); 3) 3D frameworks [ClO 4 @Sm 6 Cu 12 (OH) 24 {Cu 2 (OH)(H 2 O) 11/3 (gly) 4 } 6 Cu 5 ] 21+ and [ClO 4 @Nd 6 Cu 12 (OH) 24 {Cu 2 (OH)(H 2 O) 7/2 (pro) 4 } 6 Cu 6 ] 21+ , [ClO 4 @Er 6 Cu 12 (OH) 24 {Cu 2 (OH)(Hgly) 1/3 (gly) 4 (H 2 O) 11/3 } 6 Cu 6 ] 31+ , [ClO 4 @Ln 6 Cu 12 (OH) 24 {Cu 2 (OH)(gly) 2 (β‐ala)(H 2 O) 2 } 6 ] 17+ (Ln=Tb III or Gd III ) and [ClO 4 @Ln 6 Cu 12 (OH) 24 {Cu 2 (OH)(gly) 4/3 (β‐ala) 5/3 (H 2 O) 2 } 6 ] 17+ (Ln=Sm III or Pr III ) . In these structures, the multidimensional connectivity is realized through Cu II centers in square‐planar environments, which are linked by two bidentate amino acid ligands.…”