Coordination motifs of binary neodymium(III) D-gluconate, D-galactonate and L-gulonate complexes and the transition from inner- to outer-sphere coordination in neutral to strongly alkaline medium

Böszörményi, Éva; Dömötör, Orsolya; Kutus, Bence; Varga, Gábor; Peintler, Gábor; Sipos, Pál

doi:10.1016/j.molstruc.2022.132894

Cited by 3 publications

(7 citation statements)

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“…[56,57] After getting the value of band gap energy (E g ) using Tauc's equation, [56,57] the refractive index is calculated using the following relation [57] ðn 2 À 1Þ Judd-Ofelt parameters have been identified (see Table 5) for all synthesised compounds using the least square approach using hakU l kbi � � � � 2 values from the Carnall publication. [54] By Judd-Ofelt theory calculated value of oscillator strength (f cal ) was computed from initial (a) to excited state (b) transitions by applying equation (2). To find the accuracy of the fitting procedure, root mean square deviation (δ rms ) of f exp with respect to f cal was calculated using formula given below.…”

Section: Absorption and Emission Spectral Analysismentioning

confidence: 99%

“…value of oscillator strength (f cal ) was computed from initial (a) to excited state (b) transitions by applying equation (2). Root mean square deviation (δ rms ) of f exp with respect to f cal was calculated using equation (5).…”

Section: ¼mentioning

confidence: 99%

“…The coordination chemistry of lanthanide ions has attracted a lot of interest over the past two decades due to their advantageous magnetic, thermal, cytotoxic, redox, and optical properties as well as their enormous coordination numbers, which enable highly complex and dimensional networks to be produced. [1][2][3][4][5][6][7][8] Due to their diverse variety of distinctive properties, they have found usage in NMR imaging, sensors, the lighting sector, fibres, display devices, lasers, and biological assays. [7] Due to the low impact of the environment on 4f electrons -which are shielded by 5s 2 and 5p 6 orbitals and ionspecific emission -lanthanides normally do not promote higher covalency with ligands.…”

Section: Introductionmentioning

confidence: 99%

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Structural Features, Emission Analysis, and Covalency Comparison of Neodymium Acylpyrazolone Complexes using Oscillator Strengths, Covalency and Judd‐Ofelt Parameters**

Travadi,

Jadeja,

Butcher

2023

ChemistrySelect

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Three distorted square antiprismatic eight coordinated neodymium acylpyrazolone complexes were synthesized having the compositions [Nd(L1)3(H2O)(EtOH)] (NdL1), [Nd(L2)3(H2O)(EtOH)] (NdL2), and [Nd(L3)3(H2O)(EtOH)] (NdL3). The structure of all three complexes was examined using ESI‐mass, FT‐IR, and thermogravimetric methods. According to the single crystal analysis of NdL1, the complex was found eight‐coordinated (NdO8) with a distorted square antiprismatic geometry. A powder XRD pattern confirmed a similar structural arrangement of the other two complexes. In electronic absorption spectra, the transition 4G5/2←4I9/2, which is close to the centre of the visible spectrum (~17,500 cm−1), exhibits hypersensitivity, which stands out in stark contrast to the behaviour of many other typically weak and reliably unchanging, typical 4f–4f transitions. Through a comparative analysis of calculated oscillator strength, Judd‐Ofelt parameters, root mean square deviation, radiative lifetime and covalency parameters in various solvents, hypersensitivity, symmetry characteristics, and covalency have been thoroughly investigated. The promotion of 4f–4f electric‐dipole intensity has been found to be particularly successful with ethanol, pyridine, DMF, and DMSO. Utilizing Judd‐Ofelt Ω4 values and Hirshfeld analysis, long‐range secondary π⋅⋅⋅π stacking or H‐bonding interactions were investigated. The intensity of emission spectra, quantum yield, stokes shift, and antenna effect energy diagram was examined using solid‐state emission spectra.

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Section: Absorption and Emission Spectral Analysismentioning

confidence: 99%

Section: ¼mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural Features, Emission Analysis, and Covalency Comparison of Neodymium Acylpyrazolone Complexes using Oscillator Strengths, Covalency and Judd‐Ofelt Parameters**

Travadi,

Jadeja,

Butcher

2023

ChemistrySelect

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“…at pH = 13 in the presence of 10% V/V D2O. black: the free ligand, red: Nd(III)-complex 116 The weakening of metal ion coordination upon rising pH is unexpected, since simultaneous ligand deprotonation becomes more favorable. This contradiction can be resolved by assuming that the deprotonation takes place on the Nd(III)-bound water molecules 31,47,112 instead of the OH moieties of the ligand.…”

Section: Model Validation Via Freezing-point Depression Measurementsmentioning

confidence: 99%

“…Table 9. Stability product (log β) of Nd(III) complexes forming with different hydroxycarboxylic acids (indicated as L -) under the indicated conditions 116 . Strong chiral perturbation can be observed in the spectra of the complexes registered at nearly neutral pH.…”

Section: Model Validation Via Freezing-point Depression Measurementsmentioning

confidence: 99%

Complex equilibria in strongly alkaline aqueous solutions containing Ca(II), Nd(III) and gluconate ions

Böszörményi

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A polihidroxi-karbonsavak, mint például a glükonát (Gluc– ), alapvető szerepet játszanak különböző ipari folyamatokban. A Gluc– komplexképző tulajdonsága miatt nagy mennyiségben kerül felhasználásra: erre példa a NaGluc, ami egy gyakori adalékanyag az építőiparban, és a cement bizonyos tulajdonságainak javítására használják. Az alacsony és közepes aktivitású radioaktív hulladéktárolókban (LL/IL) a tartályokat cementtel töltik fel a szivárgás megakadályozása érdekében, de vízbetörés esetén az erősen lúgos kémhatású pórusvíz elősegítheti, hogy a Gluc– komplexálja a fémionokat, ezért ezeket a komplexképző folyamatokat az elmúlt évtizedekben kitüntetett figyelemmel kísérték és behatóan tanulmányozták. A Gluc– bizonyítottan stabil komplpexeket képez alkáli-földfém (Ca(II), Mg(II)) és átmeneti (Cu(II), Co(II), Ni(II), Mn(II), Zn(II)) fémionokkal, ezért nem zárható ki, hogy képes a három-, és négyvegyértékű aktinoidák és lantanoidák oldhatóságának növelésére. A radioaktív hulladéktárolókra jellemző oxigénszegény környezet biztosítja, hogy az aktinoida fémionok főként redukált oxidációs állapotban (Cm(III), Am(III), Pu(III), Pu(IV)) legyenek jelen. Lehetséges komplexképző anyagok is jelen vannak ezekben a tárolókban; erre példa a cellulóz tartalmú komponensek illetve szennyező anyagok bomlásával keletkező izoszacharinát (Isa– ) vagy cementadalékként a rendszerbe kerülő Gluc– . Kiemelt fontosságú tehát annak vizsgálata, hogy ezek a ligandumok képesek-e fokozni az aktinoida fémionok oldhatóságát vízbetörés esetén, mivel a radioaktív fémionok oldhatósága szerves részét képezi a radioaktív hulladék elhelyezésével kapcsolatos kockázatbecslésnek. A stabil (III) oxidációs állapotú lantanoidák és a három vegyértékű aktinoidák között fennálló kémiai hasonlóságok miatt utóbbiak modellezhetők kevésbé körülményesen vizsgálható lantanoidákkal. A radioaktív hulladéktárolókban végbemenő lehetséges komplexképződési folyamatok egyszerűsített és releváns modelljének felállításához felhasználták már a neodímiumot (Nd(III)) és a Gluc– -ot vizesközegű mérésekhez, de a lúgos kémhatású oldatokban lejátszódó folyamatok kevésbé ismertek.

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Complex Formation in Hyperalkaline Solutions

Kutus,

Sipos

2023

Metal Ions and Complexes in Solution

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Strongly alkaline conditions in aqueous systems may give rise to the formation of novel, so far undiscovered metal complexes, and crystallization from these systems often yields solid materials with peculiar local structures. This is of particular importance from a practical point of view, since the knowledge of the structure and dynamics of these solution species could be the key to understand and to manipulate a large variety of processes, both industrial and geochemical. The current contribution is focused on solution species with ligands as hydroxides, organic molecules with O-donor atoms, or both, which do not form or are undetectable at moderate pH. The possible formation of polynuclear complexes as well as various dehydration products is also discussed. A further important aspect is the characterization of the solids obtained from these systems in terms of both the local symmetry of the complexing ion, i.e. interrelations between solution and the solid structure or the lack of them, and their morphology and/or composition. The general theme of this chapter is that hyperalkalinity, an extreme condition, and unusual chemical events are expected to occur under such conditions.

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Coordination motifs of binary neodymium(III) D-gluconate, D-galactonate and L-gulonate complexes and the transition from inner- to outer-sphere coordination in neutral to strongly alkaline medium

Cited by 3 publications

References 42 publications

Structural Features, Emission Analysis, and Covalency Comparison of Neodymium Acylpyrazolone Complexes using Oscillator Strengths, Covalency and Judd‐Ofelt Parameters**

Structural Features, Emission Analysis, and Covalency Comparison of Neodymium Acylpyrazolone Complexes using Oscillator Strengths, Covalency and Judd‐Ofelt Parameters**

Complex equilibria in strongly alkaline aqueous solutions containing Ca(II), Nd(III) and gluconate ions

Complex Formation in Hyperalkaline Solutions

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