Trimethyltriazacyclohexane coordination chemistry of simple rare-earth metal salts

Wedal, Justin C.; Evans, William J.

doi:10.1039/d3dt00242j

Cited by 7 publications

(9 citation statements)

References 58 publications

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“…Ce III –O (hydroxide) distances in the present cluster are more elongated than the Ce IV –O (hydroxide) distances in reported hexanuclear clusters such as [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 4 (O 2 CtBu) 12 (L 1 ) 2 ] (2.360(8)–2.457(8) Å; L 1 = diethylenetriamine) and [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 10 (NO 3 ) 4 ] (2.384(5)–2.481(6) Å), ,, in agreement with the assigned trivalent oxidation sate for Ce in clusters in the present study. The average La–O (OTf) distance in the hexanuclear La III -cluster is similar to the average La–O (OTf) length of 2.565(3) Å in the reported tetranuclear La III -cluster, [(Me 3 tach) 4 La 4 (OH) 4 (OTf) 6 ] (Me 3 tach = trimethyltriazacyclohexane), consistent with the assigned trivalent oxidation state for La in the hexa-nuclear cluster.…”

Section: Resultssupporting

confidence: 82%

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures

Bokouende,

Kulasekara,

Worku

et al. 2023

Inorg. Chem.

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Low-valent f-block metals have intrinsic luminescence, electrochemical, and magnetic properties that are modulated with ligands, causing the coordination chemistry of these metals to be imperative to generating critical insights needed to impact modern applications. To this end, we synthesized and characterized a series of twenty-seven complexes of f-metal ions including Eu II , Yb II , Sm II , and U III and hexanuclear clusters of La III and Ce III to study the impact of tris[2-(2-methoxyethoxy)ethyl]amine, a flexible acyclic analogue of the extensively studied 2.2.2cryptand, on the coordination chemistry and photophysical properties of low-valent f-block metals. We demonstrate that the flexibility of the ligand enables luminescence tunability over a greater range than analogous cryptates of Eu II in solution. Furthermore, the ligand also displays a variety of binding modes to f-block metals in the solid state that are inaccessible to cryptates of low-valent f-block metals. In addition to serving as a ligand for f-block metals of various sizes and oxidation states, tris[2-(2methoxyethoxy)ethyl]amine also deprotonates water molecules coordinated to trivalent triflate salts of f-block metal ions, enabling the isolation of hexanuclear clusters containing either La III or Ce III . The ligand was also found to bind more tightly to Yb II and U III in the solid state compared to 2.2.2-cryptand, suggesting that it can play a role in the isolation of other low-valent f-block metals such Cf II , Np III , and Pu III . We expect that our findings will inspire applications of tris[2-(2-methoxyethoxy)ethyl]amine in the design of light-emitting diodes and the synthesis of extremely reducing divalent f-block metal complexes that are of interest for a wide range of applications.Article pubs.acs.org/IC

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Section: Resultssupporting

confidence: 82%

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures

Bokouende,

Kulasekara,

Worku

et al. 2023

Inorg. Chem.

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“…The Yb 3+ ion in the complex cation is coordinated by two Me 3 tach ligands in a bent pseudosandwich fashion (∠Me 3 tach centroid –Yb–Me 3 tach centroid = 136.7°), while two chloride ligands are located in the bisector plane (CN = 8). Structurally similar R 3 tach-based bent pseudosandwich cations were previously reported for yttrium ([YMe 2 (Me 3 tach) 2 ] + , [Y(PhCC) 2 (Me 3 tach) 2 ] + , [YMe 2 (Cy 3 tach) 2 ] + , neodymium and samarium ([LnI 2 (Me 3 tach) 2 ] + , Ln = Nd, Sm. ,, However, an REE ion was not present in the corresponding anion in any of the above examples. The ytterbium center in the [YbCl 4 (Me 3 tach)] − anion is seven-coordinate.…”

Section: Resultssupporting

confidence: 79%

“…The La1 complex was recently reported by Evans and coworkers 31 However, the structure of La1 described in that paper belongs to the P 6 3/m space group and is isomorphous to the Ln1 complexes (except La1) in our current study. The different crystallization method from toluene/hexane mixture in our case and from THF/hexane mixture 31 probably led to the formation of different solvatomorphs.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The formation of such a complex was shown earlier in this reaction. 31 Apparently, the reason for the similar behavior of holmium and yttrium chlorides is the closeness of the values of the ionic radii of Ho and Y. 34 Since the binuclear Ln2 complexes have lower Me 3 tach:Ln ratios than the Ln1 complexes, it was intriguing to investigate the possibility of forming similar binuclear complexes for early lanthanides with larger ionic radii, where the Ln1-type structures were successfully realized.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…It is worth noting that while this work was in progress two papers were published, describing the synthesis and structure of MI 3 (M = U, Np, Pu, La, Ce, Nd), LaX 3 (X = Cl, CF 3 SO 3 ), and YCl 3 adducts with the Me 3 tach ligand. , In this paper, we report on our systematic investigation of the complexes formed by the complete series of 4-f element chlorides with the Me 3 tach ligand. Our study highlights the synthesis and structural features of these complexes in the solid and solution phases.…”

Section: Introductionmentioning

confidence: 99%

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Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes

Degtyareva,

Bardonov,

Afanaseva

et al. 2024

Inorg. Chem.

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LnCl 3 (THF) 3 (Ln = Y, La ÷ Nd, Sm ÷ Lu) readily react with the tridentate 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me 3 tach) ligand to form mono-or binuclear lanthanide trichloride complexes, depending on the stoichiometry of the reaction and the ionic radius of the metal: mononuclear pseudosandwich [LnCl 3 (Me 3 tach) 2 ], (Ln = Y, La ÷ Ho) or binuclear complexes [Ln 2 Cl 6 (Me 3 tach) 3 ], or [LnCl 3 (Me 3 tach)(THF)] 2 (Ln = Sm, Tb). Detailed analysis of the NMR data of [LnCl 3 (Me 3 tach) 2 ] complexes with paramagnetic lanthanide ions showed that their structures remained unchanged in the toluene solution. A series of isomorphous complexes [LnCl 3 (Me 3 tach)(Py) 2 ] (Ln = La, Sm, Tb, Er, Lu; Py = pyridine) have been obtained by the recrystallization of either mononuclear or binuclear complexes from pyridine. Complexes of terbium and europium ions with the Me 3 tach ligand exhibit relatively high quantum yields of metal-centered luminescence (0.39 and 0.32, respectively).

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Understanding the Coordination Chemistry and Structural and Photophysical Properties of Eu^II- and Sm^II-Containing Complexes of Hexamethylhexacyclen and Noncyclic Tetradentate Amines

Bokouende,

Ward,

Allen

2024

Inorg. Chem.

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Trimethyltriazacyclohexane coordination chemistry of simple rare-earth metal salts

Abstract: Reactions of 1,3,5-trimethyl-triazacyclohexane (Me3tach) with common rare-earth iodide, chloride, and triflate salts were examined to determine the capacity of this inexpensive chelate to provide alternative precursors for THF-free reactions. The...

Cited by 7 publications

References 58 publications

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures

Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes

Understanding the Coordination Chemistry and Structural and Photophysical Properties of Eu^II- and Sm^II-Containing Complexes of Hexamethylhexacyclen and Noncyclic Tetradentate Amines

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Trimethyltriazacyclohexane coordination chemistry of simple rare-earth metal salts

Abstract: Reactions of 1,3,5-trimethyl-triazacyclohexane (Me3tach) with common rare-earth iodide, chloride, and triflate salts were examined to determine the capacity of this inexpensive chelate to provide alternative precursors for THF-free reactions. The...

Cited by 7 publications

References 58 publications

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures

Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes

Understanding the Coordination Chemistry and Structural and Photophysical Properties of EuII- and SmII-Containing Complexes of Hexamethylhexacyclen and Noncyclic Tetradentate Amines

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Understanding the Coordination Chemistry and Structural and Photophysical Properties of Eu^II- and Sm^II-Containing Complexes of Hexamethylhexacyclen and Noncyclic Tetradentate Amines