Mechanochemical Syntheses of Ln(hfac)3(H2O)x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)n Complexes

Chappidi, Deepthi Y.; Gordon, Matthew N.; Ashberry, Hannah M.; Huang, Junjie; Labedis, Bruce M.; Cooper, Riley E.; Cooper, Brandon J.; Carta, Veronica; Skrabalak, Sara E.; Dunbar, Kim R.; Fatila, Elisabeth M.

doi:10.1021/acs.inorgchem.2c01274

Cited by 6 publications

(10 citation statements)

References 48 publications

(78 reference statements)

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“…A six-membered chelate ring (La···O–P–C–C–O) is formed on binding the O2-donors, originating from the pyrazolone backbone and the phosphoryl group, with the La(III) cation. Compared to Eu(III) and Yb(III), lighter La(III) has a tendency to adopt a higher coordination number (and often a more varied coordination geometry) due to its larger ionic radius and lower charge-to-radius ratio . The respective distances for Ln···O and O C ···O P are listed in Table S1, and the average values are listed in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Compared to Eu(III) and Yb(III), lighter La(III) has a tendency to adopt a higher coordination number (and often a more varied coordination geometry) due to its larger ionic radius and lower charge-to-radius ratio. 45 The respective distances for Ln•••O and O C •••O P are listed in Table S1, 43 and the average values are listed in Table 1.…”

Section: Synthesis Of 4-phosphoryl Pyrazolonementioning

confidence: 99%

“…Yield: 0.45 g (18%); mp 101−103 °C; Raman (80 mW, in cm −1 ) ν: 3074 (38), 3064 (42), 3035 (15), 2987 (16), 2958 (46), 2923 (42), 2858 (35), 1598 (100), 1550 (9), 1527 (27), 1492 (13), 1438 (45), 1400 (32), 1371 (19), 1325 (22), 1300 (9), 1180 (6), 1161 (20), 1051 (10), 1024 (14), 1010 (11), 999 (61), 850 (15), 715 (9), 642 (18), 615 (15), 436 (6), 266 (6), 247 (6), 148 (11), 117 (13), 75 (74); IR (ATR, in cm −1 ) ν: 2955 (vw), 2856 (vw), 2490 (vw), 1599 (w), 1549 (m), 1531 (m), 1491 (w), 1460 (w), 1437 (w), 1400 (w), 1369 (vw), 1325 (w), 1298 (vw), 1265 (vw), 1188 (s), 1165 (m), 1092 (w), 1070 (w), 1051 (w), 1011 (vs), 924 (vw), 833 (w), 804 (vs), 768 (s), 712 (m), 692 (s), 654 (w), 642 (vw), 607 (m), 552 (vs), 511 (m), 434 (m); 1 H NMR (CDCl 3 , 300 K, in ppm): δ 2.26 (3H, d, 4 J HP = 0.8 Hz, H4), 3.76 (6H, d, 3 J HP = 11.7 Hz, H5), 7.28 (1H, mt, 3 J HH = 7.5 Hz, H10), 7.43 (2H, mt, 3 J HH = 8.0 Hz, H9), 7.77 (2H, md, 3 J HH = 7.6 Hz, H8); 13 C{ 1 H} NMR (CDCl 3 , 300 K, in ppm): δ 14.0 (1C, s, C4), 52.9 (2C, d, 2 J CP = 5 Hz, C5), 82.6 (1C, d, 1 J CP = 219 Hz, C2), 121.5 (2C, s, C8), 126.8 (1C, s, C10), 129.2 (2C, s, C9), 137.8 (1C, s, C7), 149.6 (1C, d, 2 J CP = 10 Hz, C3), 159.8 (1C, d, 2 J CP = 23 Hz, C1); 31 (2-ethylhexyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)phosphonate HL 3 .…”

Section: Synthesis Of Dimethyl(5-hydroxy-3-methyl-1phenyl-1hpyrazol-4...mentioning

confidence: 99%

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Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation

et al. 2023

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Highly selective rare-earth separation has become increasingly important due to the indispensable role of these elements in various cutting-edge technologies including clean energy. However, the similar physicochemical properties of rare-earth elements (REEs) render their separation very challenging, and the development of new selective receptors for these elements is potentially of very considerable economic and environmental importance. Herein, we report the development of a series of 4-phosphoryl pyrazolone receptors for the selective separation of trivalent lanthanum, europium, and ytterbium as the representatives of light, middle, and heavy REEs, respectively. X-ray crystallography studies were employed to obtain solid-state structures across 11 of the resulting complexes, allowing comparative structure–function relationships to be probed, including the effect of lanthanide contraction that occurs along the series from lanthanum to europium to ytterbium and which potentially provides a basis for REE ion separation. In addition, the influence of ligand structure and lipophilicity on lanthanide binding and selectivity was systematically investigated via n-octanol/water distribution and liquid–liquid extraction (LLE) studies. Corresponding stoichiometry relationships between solid and solution states were well established using slope analyses. The results provide new insights into some fundamental lanthanide coordination chemistry from a separation perspective and establish 4-phosphoryl pyrazolone derivatives as potential practical extraction reagents for the selective separation of REEs in the future.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of 4-phosphoryl Pyrazolonementioning

confidence: 99%

Section: Synthesis Of Dimethyl(5-hydroxy-3-methyl-1phenyl-1hpyrazol-4...mentioning

confidence: 99%

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Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation

et al. 2023

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“…The speciation of [Ln(ttfa) 3 ) 2 ] complexes has been widely reported in the literature [46][47][48][49][50][51] and it is known that at very low concentrations complex mixtures can occur through dissociation of one or more of the ligands. Our study within reports these results with care and does not discount the possibility of some dissociation.…”

Section: (4 Of 9)mentioning

confidence: 99%

Solution‐State Cooperative Luminescence Upconversion in Molecular Ytterbium Dimers

Soro

Knighton

Avecilla

et al. 2022

Advanced Optical Materials

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anti-Stokes emission, UC is a process of choice for bio-analytical applications, removing spurious signals originating from autofluorescence of the samples and light scattering. Consequently, UC has found many applications such as in microscopy and photodynamic therapy, [2] remote cellular activation, [3] or bioassays. [4,5] However, these processes are typically observed in solid-state materials [6] or nanoparticles, [7] but a seminal example of energy transfer UC (ETU) at the molecular scale was reported by Piguet and co-workers in 2011, which consisted of a triply stranded Cr III -Er III -Cr III helicate. [8,9] In the subsequent years this has been expanded to encompass a range of discrete upconverting systems, operating by excited state absorption (ESA), [10][11][12] energy transfer UC, or cooperative sensitizaton (CS). [15][16][17][18] At the molecular scale, much attention must be paid to minimize quenching due to the increased prevalence of nonradiative de-excitation processes from molecules in solution, primarily through OH, NH, and CH oscillators in the first or second coordination sphere. [20][21][22] This is achieved by using sterically encumbering ligand systems, [23] deuteration of the ligand scaffold, [16] or using perdeuterated solvents. [16,24,25] One key impediment in the development of new molecular UC devices is the typical requirement to prepare heterometallic polyads, as is the case with CS systems comprising two or more Yb III sensitizers around Tb III or Ru II acceptors (Figure 1a). [17,26] This approach, despite its effectiveness, is onerous due to the similar chemical reactivity between lanthanides, [27,28] as is the case for mixed Yb/Tb systems, which constrains the synthetic accessibility. [15,16] Inspired by the pioneering work by Auzel [29] on solid-state materials, [30,31] we reported the first example of solution-state molecular cooperative luminescence (CL) using a Yb 9 cluster. [32] This entails double excitation of two proximate Yb III ions at 980 nm which produces emission from a virtual excited state at 503 nm via a two-photon process (Figure 1b). While it is a key tenet of UC processes that the efficiency of UC is improved using more donor ions, there also remains the possibility of concentration quenching, which has been observed in nanoparticles. [33,34] Furthermore, the two-photon power dependence of the UC observed in homo-nonanuclear Yb 9 clusters supports the accepted mechanism of the requirement of only two proximate Yb III ions. Conclusive confirmation of this dinuclear mechanism can only occur through removal of the extraneous Yb III donors to its fundamental form in a dimeric Yb 2 system (lex parsimoniae). This strategy is not feasible in either Two homometallic ytterbium dimers are prepared and their solution-state photoluminescence and upconversion properties are investigated. Both complexes exhibit two-photon cooperative luminescence upconversion in the visible region (λ em ≈ 510 nm) upon excitation into the near-infrared Yb 2 F 5/2 ← 2 F 7/2 absorption band at 98...

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“…S2 (ESI †). 55 Synthesis of LnHPMO. The materials were synthesised in Pyrex test tubes using a heating block.…”

mentioning

confidence: 99%

Periodic mesoporous organosilica based sensor for broad range mercury detection by simultaneous downshifting/upconversion luminescence

et al. 2023

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Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes

Cited by 6 publications

References 48 publications

Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation

Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation

Solution‐State Cooperative Luminescence Upconversion in Molecular Ytterbium Dimers

Periodic mesoporous organosilica based sensor for broad range mercury detection by simultaneous downshifting/upconversion luminescence

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