TY - JOUR
T1 - Structural analysis and photoluminescence properties of low dimensional lanthanide tetracyanometallates
AU - Stojanovic, Milorad
AU - Robinson, Nicholas J.
AU - Assefa, Zerihun
AU - Sykora, Richard E.
PY - 2011/10/1
Y1 - 2011/10/1
N2 - The synthesis of a number of lanthanide tetracyanometallate (TCM) compounds have been carried out by reaction of Ln3+ nitrate salts and potassium tetracyanometallates in solvent systems containing dimethylsulfoxide and water. These reactions result in the isolation of three distinct structure types: (1) monoclinic [Ln(DMSO)4(H2O)3M(CN) 4](M(CN)4)0.5·2H2O (Ln = Eu, Tb and M = Pd, Pt), (2) orthorhombic {La(DMSO)3(H2O) 2(NO3)M(CN)4}∞·H 2O (M = Pd, Pt), and (3) orthorhombic {Ln(DMSO)3(H 2O)(NO3)M(CN)4}∞ (Ln = Tb and M = Pd, Pt; Ln = Er, Yb and M = Pt) in the form of single crystals. Single-crystal X-ray diffraction has been used to investigate their structural features. Structure type 1 is a zero dimensional ionic compound with a M/Ln ratio of 1.5:1. It contains coordinated as well as uncoordinated [M(CN) 4]2- (M = Pd, Pt) anions and features relatively long platinophilic interactions. Structure types 2 and 3 differ quite drastically from structure type 1, but they are very similar to each other. Both of the latter are one-dimensional in nature due to chains containing linkage of Ln 3+ coordination spheres with trans-bridging [M(CN)4] 2- anions. These coordination polymers both have a M/Ln ratio of 1:1, a lack of platinophilic interactions, and incorporation of a bidentate NO 3- for charge balance. Photoluminescence properties for select Eu3+ and Tb3+ compounds have been investigated. They show characteristic absorption and emission for the Ln3+ ions, but no significant influence of the tetracyanometallate anions.
AB - The synthesis of a number of lanthanide tetracyanometallate (TCM) compounds have been carried out by reaction of Ln3+ nitrate salts and potassium tetracyanometallates in solvent systems containing dimethylsulfoxide and water. These reactions result in the isolation of three distinct structure types: (1) monoclinic [Ln(DMSO)4(H2O)3M(CN) 4](M(CN)4)0.5·2H2O (Ln = Eu, Tb and M = Pd, Pt), (2) orthorhombic {La(DMSO)3(H2O) 2(NO3)M(CN)4}∞·H 2O (M = Pd, Pt), and (3) orthorhombic {Ln(DMSO)3(H 2O)(NO3)M(CN)4}∞ (Ln = Tb and M = Pd, Pt; Ln = Er, Yb and M = Pt) in the form of single crystals. Single-crystal X-ray diffraction has been used to investigate their structural features. Structure type 1 is a zero dimensional ionic compound with a M/Ln ratio of 1.5:1. It contains coordinated as well as uncoordinated [M(CN) 4]2- (M = Pd, Pt) anions and features relatively long platinophilic interactions. Structure types 2 and 3 differ quite drastically from structure type 1, but they are very similar to each other. Both of the latter are one-dimensional in nature due to chains containing linkage of Ln 3+ coordination spheres with trans-bridging [M(CN)4] 2- anions. These coordination polymers both have a M/Ln ratio of 1:1, a lack of platinophilic interactions, and incorporation of a bidentate NO 3- for charge balance. Photoluminescence properties for select Eu3+ and Tb3+ compounds have been investigated. They show characteristic absorption and emission for the Ln3+ ions, but no significant influence of the tetracyanometallate anions.
KW - Lanthanide
KW - Photoluminescence
KW - Single-crystal X-ray diffraction
KW - Tetracyanopalladate
KW - Tetracyanoplatinate
UR - https://www.scopus.com/pages/publications/80052835606
U2 - 10.1016/j.ica.2011.07.002
DO - 10.1016/j.ica.2011.07.002
M3 - Article
SN - 0020-1693
VL - 376
SP - 414
EP - 421
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1
ER -