Synthesis, characterization, and structural analyses of three high-coordination tetra-n-butylammonium lanthanide(III) complexes

Mullica, D. F.; Bonilla, Bianca M; David, Maria; Farmer, J. Matt; Kautz, Jason A.

doi:10.1016/s0020-1693(99)00177-2

Cited by 10 publications

(5 citation statements)

References 15 publications

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“…The 8 coordinate complex is best described as dodecahedral as outlined by the principles of Hoard and Silverton 37 and is isostructural to the previously reported Nd, Dy and Yb(III) lanthanide thiocyanates. 9 The complex crystallizes in the orthorhombic space group Fddd and the asymmetric unit contains half of a the isostructural Yb and Nd(III) complexes, respectively. This decrease in nitrate bond distance to Lu in 1 compared to [Yb(NCS) 4 (NO 3 ) 2 ] 3À is also apparent in the elevated O1-Lu1-O2 bite angle at 53.18(7)1 compared to 52.2(4)1 in the Yb complex and at 50.2(5)1 in the Nd complex.…”

Section: X-ray Diffractionmentioning

confidence: 99%

“…Without excess of thiocyanate ions, the isostructural [(n-C 4 H 9 ) 4 N] 3 [Nd(NCS) 2 (NO 3 ) 4 ] complex of neodymium has also been isolated. 8 Crystal structures of [(n-C 4 H 9 ) 4 N] 3 [Ln(NCS) 4 (NO 3 ) 2 ] (Ln = Nd, Dy and Yb) have also been reported 9 showing eight-fold coordination with four oxygen atoms of the bidentate nitrate groups and four thiocyanate ions bonded via the N atom. The coordination polyhedron which best represents the spatial arrangement is a dodecahedron.…”

Section: Introductionmentioning

confidence: 99%

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Crystal structure versus solution for two new lutetium thiocyanato complexes

et al. 2011

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Section: X-ray Diffractionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Crystal structure versus solution for two new lutetium thiocyanato complexes

et al. 2011

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“…During our ongoing task to explore multifunctional molecular ferroelectrics with promising applications, we realized that x and y can be varied from 0, 2, 4, to 6 (where x + y= 6) in the molecular system ( n Bu 4 N ) 3 [M(NO 3 ) x (SCN) y ] ( n Bu 4 N = tetrabutyl ammonium; M=Nd, Pr), and the coordination number of the M atoms can change from 6, 8, 10, to 12, according to the literature …”

Section: Introductionmentioning

confidence: 99%

Two Rare‐Earth Molecular Ferroelectrics with High Curie Temperatures, Large Spontaneous Polarization, Switchable Second Harmonic Generation Effects, and Strong Photoluminescence

Yang

Dong

et al. 2020

Chemistry A European J

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Smartm ultifunctional molecular ferroelectrics bearing high Curie temperatures and diverse excellent physical properties, such as second harmonic generation (SHG) responses, luminescence, and semiconductivity, among others, have significant applicationsb ut have seldom been documented. Herein, the rare-earth metals Nd and Pr are introduced into as imple molecular system (nBu 4 N) 3 [M(NO 3 ) x (SCN) y ]( nBu 4 N = tetrabutyl ammonium, M = rare-earth metal, nBu = CH 3 CH 2 CH 2 CH 2 ), and two new multifunctional molecular ferroelectrics are obtained:Their distinct heat and dielectric anomaly dependence on temperature verifies that compounds 1 and 2 experience high-temperature para-ferroelectric phase transitions at 408 and 413 K, respectively.S trikingly,b oth molecular ferroelectrics possess large spontaneousp olarizationw ith P s values of 9.05 and 8.50 mCcm À2 ,r espectively,a nd are further characterized by the appearance of multiple intersecting non-1808 domains and polarization switching behavior.I np articular,c ompounds 1 and 2 show good stability with only a small decrease in SHG intensity after switching cycles,s uggesting that they have great potentialfor applicationinnonlinear optical( NLO) switches. Simultaneously,t he rare-earth compounds 1 and 2 present brighty ellow-red andb right green fluorescence, respectively,atr oom temperature. Figure 5. UV/Vis absorptionspectra of compounds 1 (a) and 2 (c), and fluorescence emission spectraofc ompounds 1 (b) and 2 (d).

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“…8 Early lanthanides favor higher coordination numbers such as 10 in [ n Bu 4 N] 3 [Ln(NCS) 2 (NO 3 ) 4 ] (Ln = Ce, 9 Nd 10 ), while coordination number 9 is found in [Ln(18crown-6)(NCS) 3 ] (Ln = Eu, Tb). 11 Coordination number 8 is common in structures as diverse as [ n Bu 4 N] 3 [Ln-(NCS) 4 (NO 3 ) 2 ] (Ln = Nd, Dy, Yb), 12 [Ph 3 PNH 2 ][Sm-(NCS) 4 (DME) 2 ], 13 [Me 4 N] 5 [Ln(NCS) 8 ]•2Sv (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy; Sv = C 6 H 6 ), 14 the ionic liquids [Bmim] 4 [Ln(NCS) 7 (H 2 O)] (Bmim = 1-butyl-3-methylimidazolium; Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, and Yb), 15 and [C 6 mim] 5 [Dy(NCS) 8 ] (C 6 mim = 1-hexyl-3-methylimidazolium), 16 [Et 4 N] 4 [Ce(NCS) 7 (H 2 O)], 17 [Et 4 N] 3 [La-(NCS) 6 (H 2 O)(MeOH)], 18 [Et 4 N][Ln(NCS) 4 (H 2 O) 4 ] (Ln = Nd, Eu), 19 and K[Ln(NCS) 4 (H 2 O) 4 ]•3KNCS•2H 2 O (Ln = Nd, Lu). 20 Coordination numbers 7 in [Et 4 N] 4 [Ln(NCS) 7 ]•C 6 H 6 (Ln = La, Pr) 21 and 6 in [ n Bu 4 N] 3 [Ln(NCS) 6 ] (Ln = Y, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) 22 or [Et 4 N] 3 [Ln(NCS) 6 ]•S (Ln = Er, Yb; S = aromatic solvents) 23 have also been reported.…”

Section: ■ Introductionmentioning

confidence: 99%

Structural Variability of 4f and 5f Thiocyanate Complexes and Dissociation of Uranium(III)–Thiocyanate Bonds with Increased Ionicity

Biswas

Nuzzo

et al. 2017

Inorg. Chem.

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A series of complexes [EtN][Ln(NCS)(HO)] (Ln = Pr, Tb, Dy, Ho, Yb) have been structurally characterized, all showing the same structure, namely a distorted square antiprismatic coordination geometry, and the Ln-O and Ln-N bond lengths following the expected lanthanide contraction. When the counterion is Cs, a different structural motif is observed and the eight-coordinate complex Cs[Nd(NCS)] isolated. The thorium compounds [MeN][Th(NCS)(NO)] and [MeN][Th(NCS)(NO)] have been characterized, and high coordination numbers are also observed. Finally, attempts to synthesize a U(III) thiocyanate compound has been unsuccessful; from the reaction mixture, a heterocycle formed by condensation of five MeCN solvent molecules, possibly promoted by U(III), was isolated and structurally characterized. To rationalize the inability to isolate U(III) thiocyanate compounds, thin-layer cyclic voltammetry and IR spectroelectrochemistry have been utilized to explore the cathodic behavior of [EtN][U(NCS)] and [EtN][U(NCS)(bipy)] along with a related uranyl compound [EtN][UO(NCS)]. In all examples, the reduction triggers a rapid dissociation of [NCS] ions and decomposition. Interestingly, the oxidation chemistry of [EtN][UO(NCS)] in the presence of bipy gives the U(IV) compound [EtN][U(NCS)], an unusual example of a ligand-based oxidation triggering a metal-based reduction. The experimental results have been augmented by a computational investigation, concluding that the U(III)-NCS bond is more ionic than the U(IV)-NCS bond.

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Synthesis, characterization, and structural analyses of three high-coordination tetra-n-butylammonium lanthanide(III) complexes

Cited by 10 publications

References 15 publications

Crystal structure versus solution for two new lutetium thiocyanato complexes

Crystal structure versus solution for two new lutetium thiocyanato complexes

Two Rare‐Earth Molecular Ferroelectrics with High Curie Temperatures, Large Spontaneous Polarization, Switchable Second Harmonic Generation Effects, and Strong Photoluminescence

Structural Variability of 4f and 5f Thiocyanate Complexes and Dissociation of Uranium(III)–Thiocyanate Bonds with Increased Ionicity

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