Crystal structure versus solution for two new lutetium thiocyanato complexes

Lozano-Rodriguez, M. Janeth; Copping, Roy; Petit, Sébastien; Solari, Pier-Lorenzo; Guilbaud, Philippe; León, J.; Auwer, Christophe Den

doi:10.1039/c1nj20494g

Cited by 11 publications

(10 citation statements)

References 47 publications

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“…Heteroleptic metal thiocyanates can be prepared by the metathesis reactions of appropriate chloride (nitrate) hydrates with potassium thiocyanate in alcoholic solutions. Generally, metal thiocyanate hydrates are not isolated, and their alcoholic solutions are used as the starting reagents …”

Section: Resultsmentioning

confidence: 99%

“…In the series of N‐donor ligands, the thiocyanate ion NCS – occupies a special place, due to its structural features, charge distribution, and coordination capacity. The published studies of homo‐ and heteroleptic neutral and ionic rare‐earth thiocyanates are scarce . Interest in these compounds is associated with their actual and promising applications.…”

Section: Introductionmentioning

confidence: 99%

“…A quite comprehensive analysis of the literature data concerning the synthesis and structures of coordination compounds of thiocyanates was performed in ref . where the focus was on homoleptic thiocyanate compounds, whereas heteroleptic compounds have received less attention.…”

Section: Introductionmentioning

confidence: 99%

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Mononuclear Dysprosium Thiocyanate Complexes with 2,2′‐Bipyridine and 1,10‐Phenanthroline: Synthesis, Crystal Structures, SIM Behavior, and Solid‐Phase Transformations

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mononuclear Dysprosium Thiocyanate Complexes with 2,2′‐Bipyridine and 1,10‐Phenanthroline: Synthesis, Crystal Structures, SIM Behavior, and Solid‐Phase Transformations

et al. 2017

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“…In the infrared spectra, only a broad peak is observed, but the shift in frequency of the CN bond stretch is in keeping with the change in the size of the lanthanide ion, as has been noted previously. 20 Dissociation of [NCS] − was not observed, as revealed by the absence of the band at 2060 cm −1 . For 6, two bands are evident in the IR spectrum, and the Raman spectrum shows two bands at 2063 and 2052 cm −1 (Table 2).…”

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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“…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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Crystal structure versus solution for two new lutetium thiocyanato complexes

Cited by 11 publications

References 47 publications

Mononuclear Dysprosium Thiocyanate Complexes with 2,2′‐Bipyridine and 1,10‐Phenanthroline: Synthesis, Crystal Structures, SIM Behavior, and Solid‐Phase Transformations

Mononuclear Dysprosium Thiocyanate Complexes with 2,2′‐Bipyridine and 1,10‐Phenanthroline: Synthesis, Crystal Structures, SIM Behavior, and Solid‐Phase Transformations

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

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

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