Effect of lanthanide contraction on the Ln/Sb/Se/dien system: solvothermal syntheses and characterizations of lanthanide(III)-selenidoantimonate complexes with diethylenetriamine as a co-ligand

Abstract

2013) Effect of lanthanide contraction on the Ln/Sb/Se/dien system: solvothermal syntheses and characterizations of lanthanide(III)-selenidoantimonate complexes with diethylenetriamine as a coligand, Journal of Coordination Chemistry, 66:4, 650-661,The ternary system Ln/Sb/Se was investigated in a diethylenetriamine (dien) solvent under solvothermal conditions and two types of neutral lanthanide(III)-selenidoantimonate complexes [Ln(dien) 2 (μ-η 1 ,η 2 -SbSe 4 )] n (Ln = Pr(1), Nd (2)) and [Ln(dien) 2 (η 2 -SbSe 4 )] (Ln = Sm (3), Gd(4)) were prepared. The lanthanide ions form [Ln(dien) 2 ] 3+ cations with two dien chelating ligands. In 1 and 2, SbSe 3À 4 is a tridentate μ-η 1 ,η 2 -SbSe 4 bridging ligand to connect [Ln(dien) 2 ] 3+ into onedimensional coordination polymers [Ln(dien) 2 (μ-η 1 ,η 2 -SbSe 4 )] n ; it coordinates to [Sm(dien) 2 ] 3+ and [Gd(dien) 2 ] 3+ as a η 2 -SbSe 4 bidentate chelating ligand, forming 3 and 4. Ln 3+ in 1-2 and 3-4 are nine-and eight-coordinate environments, forming distorted monocapped square antiprisms and bicapped trigonal prisms, respectively. The different coordination modes of SbSe 3À 4 between 1-2 and 3-4 are related to size of Ln 3+ . Complexes 1-4 exhibit semiconducting properties with band gaps of 2.08-2.28 eV.

Solvothermal syntheses, crystal structures, and properties of new lanthanide compounds based on tetraselenidoantimonate and tetraethylenepentamine mixed ligands

“…The Table S6). The NÁÁÁSe separations and N-HÁÁÁSe angles are in agreement with reported values observed in Ln tetraselenidoantimonate containing amino coligands [41][42][43][44]48]. The layers are further connected through interlayer N-HÁÁÁSe interactions to form a 3-D H-bonding network (Fig.…”

“…ions and chalcogenidoantimonate anions via TM-S or TM-Se bond, the weak interactions between lanthanide (Ln) ions and chalcogenidoantimonate anions make the synthesis of ternary Ln-chalcogenidoantimonates a challenging task. However, our work has demonstrated that the chalcogenidoantimonate anions [SbS 4 ] 3-and [SbSe 4 ] 3-can coordinate to Ln(III) centers using coordinative amines as co-ligands, and a number of Ln-chalcogenidoantimonates have been solvothermally prepared in en, dien, and trien solvents [39][40][41][42][43][44]. Unlike the TM n?…”

“…centers via Ln-S or Ln-Se bond formation. Furthermore, the [SbS 4 ] 3-or [SbSe 4 ] 3-anions can be tuned to coordinate to Ln(III) centers in mono-SbQ 4 , 1j 2 -SbQ 4 and l-1j,2j 2 -SbQ 4 (Q=S, Se) coordination modes using ethylene polyamines en, dien and trien as the co-ligands [39][40][41][42][43][44]. It is important to systematically investigated the synergistic coordination effects of SbQ 4 and polyamino ligands on the Ln(III) centers in the preparation of new Ln-containing chalcogenidometalates.…”

“…Ln-N 76.9 (3)-151.2(3) 77.0 (3)-150.9 (3) 76.9 (3)-150.7 (3) N-Ln-N 66.2 (4)-140.8(4) 66.8 (3)-141.2 (4) 67.0 (4)-141.0 (4) Se-Ln-N 82.1 (2)-147.9 (2) 81.8 (3)-143.5 (2) 81.5 (3)-148.ethylene polyamino coligands like en, dien, trien or their mixtures[41][42][43][44]. Being multidentate chelating ligands with N-donor atoms, ethylene polyamines are prone to chelating the Ln(III) ions, but usually leave one or more coordination sites free due to steric hindrance of the polyamines.The numbers of left coordination sites are related to the structure of ethylene polyamine and the size of Ln(III) ion.…”

A novel samarium complex with interesting photoluminescence and semiconductive properties

“…A search from the Cambridge Crystallographic Data Centre (CCDC) shows that there are dozens of complexes containing samarium [36][37][38][39][40]. However, among these complexes, only several are samarium-containing complex with bipy [41][42][43][44][45].…”