Thermochemistry study and improved thermal stability of Yb14MnSb11 alloyed by Ln3+ (La–Lu)

Vasilyeva, I.G.; Nikolaev, R. E.; Abdusaljamova, M. N.; Kauzlarich, Susan M.

doi:10.1039/c6tc00178e

Cited by 21 publications

(24 citation statements)

References 15 publications

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“…79 Additionally, the lighter rare earths affect the rate of oxidation, forming a protective oxide surface. 80 In the case of A14-xRExMSb11, the effect of a 3+ rare earth depends upon the RE cation and the element in the A site The amount of RE appears to be limited to x ~ 0.5 in the case of Yb14-xRExMnSb11, 31,[59][60][61][62][63][64]78 however, in the case of Ca14-xRExMnSb11 and Ca14-xRExMnBi11, the amount of x appears to be closer to 1. 65,66 Solid solutions on the M site have focused on Mn-Zn and Mn-Al.…”

Section: A14mpn11 Structure Typementioning

confidence: 98%

“…Site preferences are observed in the occupancy of the cation sites when doping or alloying on the A position. 31,[59][60][61][62][63][64][65][66] The tendency is for smaller atoms to prefer the A1 and A3 sites, and for larger atoms to prefer the A2 and A4 sites. This can be understood through the Hirshfeld surface analysis of chemical bonding.…”

Section: A14mpn11 Structure Typementioning

confidence: 99%

“…[75][76][77] More recently, the solid solutions of the A site have focused on RE (rare earth) substitutions. 31,[59][60][61][62][63][64][65][66]78 As mentioned above, the rare earth elements in the 3+ oxidation state (RE) show site preferences that depend upon size. The identity of the 3+ rare earth element affects the sublimation temperature and melting point with the lighter rare earths providing higher melting points and lower vapor pressures.…”

Section: A14mpn11 Structure Typementioning

confidence: 99%

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The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Cerretti

Wille

et al. 2019

Journal of Solid State Chemistry

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Yb14MnSb11 is a member of a remarkable structural family of compounds that are classified according to the concept of Zintl. This structure type, of which the prototype is Ca14AlSb11, provides a flexible framework for tuning structure-property relationships and hence the physical and chemical properties of compounds. Compounds within this family show exceptional high temperature thermoelectric performance at temperatures above 300 K and unique magnetic and transport behavior at temperatures below 300 K. This review provides an overview of the structure variants, the magnetic properties, and the thermoelectric properties. Suggestions for directions of future research are provided. One active research area is to systematically explore more complex compositions such as Ca11Sb10, K4Pb9, Na8Si46, Ca14AlSb11 and KBa2InAs3. 3-7 The other direction is to replace the alkaline earth metals with divalent rare earth elements (Sm, Eu and Yb) along with the introduction of transition metals into structures, typically replacing the less electronegative metalloid in the anionic framework. 8-10 Combinations of these two directions led to compounds such as Yb14MnSb11, Pr4MnSb9, Eu10Mn6Sb13, Yb9Zn4+xBi9 and Cs13Nb2In6As10. 11-16 The complexity of compositions can be combined with a small flexibility in electron counting. For example, Yb14MnSb11 and Yb9Zn4+xBi9 do not strictly follow the Zintl-Klemm concept. Yb14MnSb11 has Mn 2+ instead of a group 13 element such as in Ca14AlSb11 and therefore is electron deficient, 17 and Yb9Zn4+xSb9 has interstitial Zn atoms which can be compositionally varied to achieve specific properties. 18 At the same time, the total number of valence electrons within an identical Zintl phase structure type with different elements may also vary slightly but the variance can be quite small and limited for many structure types that can be described by the Zintl concept. Therefore, with the introduction of transition elements, new electronic properties are possible, but complete transfer of electrons and clear counting of valence electrons remains a criterion for describing transition and rare earth metal containing Zintl phase compounds. Binary Zintl phase compounds which have compositions of simple ratios of elements usually adopt the structures of known oxides or halides, in which anions and cations are isolated in the structure with no covalent bonding. 2, 19 Both isolated anions, polyanions or clusters in Zintl phase compounds can provide complex compositions such as those represented by Ca11Sb10 and K4Pb9. 3, 4 Polyanions or clusters are formed to compensate for lack of enough electrons from the electropositive element to satisfy valence to form a simple one atom anion. Sb forms Sb-Sb single bonds in the Ca11Sb10 structure type resulting in Sb2 4and Sb4 2polyanions in the structure. 3 The Zintl electron counting provides the following charge balanced scenario: 11Ca 2+ + 4Sb 3-+ 2Sb2 4-+ Sb4 2-. Two types of clusters exist in K4Pb9 with the same formal oxidation state: a monocapped square antiprism and a tr...

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Section: A14mpn11 Structure Typementioning

confidence: 98%

Section: A14mpn11 Structure Typementioning

confidence: 99%

Section: A14mpn11 Structure Typementioning

confidence: 99%

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The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Cerretti

Wille

et al. 2019

Journal of Solid State Chemistry

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“…The 4 Yb sites in Yb14MSb11 are often compared by the volume of the polyhedron between each Yb and its nearest neighbour Sb atoms. 12,22 Figure 3 shows the Yb site polyhedral volumes for the Mg, Mn, and Zn analogs. Yb14MgSb11 exhibits the largest volumes for each cation site, with Yb4 showing the largest volume difference between Mg and its Mn and Zn counterparts.…”

mentioning

confidence: 99%

Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb₁₄MgSb₁₁

Wille

Fettinger

et al. 2018

Chem. Commun.

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“…Consequently, D-π-A dyes are of considerable practical concern as useful fluorescence sensors for cation, anion and neural species [5][6][7][8][9][10][11][12][13][14], efficient emitters for organic light emitting diodes (OLEDs) [15][16][17][18][19][20][21][22][23][24], and promising photosensitizers for dye-sensitized solar cells (DSSCs) [25][26][27][28][29][30][31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photophysical and Electrochemical Properties of Pyridine-, Pyrazine- and Triazine-based (D-π-)₂A Fluorescent Dyes

Imato¹,

Enoki²,

Uenaka³

et al. 2019

Preprint

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Donor–acceptor–π-conjugated (D–π–)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2 with two (diphenylamino)carbazole-thiophene units as D (electron-donating group)–π (π-conjugated bridge) moiety and a pyridine, pyrazine or triazine ring as electron-withdrawing group (electron-accepting group; A) have been designed and developed and their photophysical and electrochemical properties were investigated based on the photoabsorption and fluorescence spectroscopy, Lippert–Mataga plots, cyclic voltammetry and density functional theory calculations. The photoabsorption maximum (λ abs max) and the fluorescence maximum (λ fl max) for the intramolecular charge-transfer characteristic band of the (D–π–)2A fluorescent dyes show bathochromic shift in the order of OUY-2 < OUK-2 < OUJ-2. Moreover, the photoabsorption spectra of the (D–π–)2A fluorescent dyes are nearly independent of solvent polarity, while their fluorescence maxima bathochromically shifted with increasing solvent polarity (i.e., positive fluorescence solvatochromism). The Lippert–Mataga plots for OUY-2, OUK-2 and OUJ-2 indicate that the Δμ (= μ e ‒ μ g) value, which is the difference in the dipole moment of the dye between the excited (μ e) and the ground (μ g) states, increases in the order of OUY-2 < OUK-2 < OUJ-2, that is, the fact explains our findings that OUJ-2 shows large bathochromic shifts in their fluorescence maxima in polar solvents and that the Stokes shift values for OUJ-2 in polar solvents are much larger than those in nonpolar solvents. The cyclic voltammetry of OUY-2, OUK-2 and OUJ-2 demonstrated that there is little difference in the HOMO energy level among the three dyes, but the LUMO energy levels decrease in the order of OUY-2 > OUK-2 > OUJ-2. Consequently, this work reveals that for the (D–π–)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2 the bathochromic shifts of λ abs max and λ fl max and the lowering of the LUMO energy level are dependent on the electron-withdrawing ability of azine ring, which increases in the order of OUY-2 < OUK-2 < OUJ-2.

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Thermochemistry study and improved thermal stability of Yb₁₄MnSb₁₁ alloyed by Ln³⁺ (La–Lu)

Abstract: Increase in melting points of Yb13.6Ln0.4MnSb11 due to the Ln ordered distribution and ionic bond strengthening.

Cited by 21 publications

References 15 publications

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb₁₄MgSb₁₁

Synthesis and Photophysical and Electrochemical Properties of Pyridine-, Pyrazine- and Triazine-based (D-π-)₂A Fluorescent Dyes

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Thermochemistry study and improved thermal stability of Yb14MnSb11 alloyed by Ln3+ (La–Lu)

Abstract: Increase in melting points of Yb13.6Ln0.4MnSb11 due to the Ln ordered distribution and ionic bond strengthening.

Cited by 21 publications

References 15 publications

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

The remarkable crystal chemistry of the Ca14AlSb11 structure type, magnetic and thermoelectric properties

Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb14MgSb11

Synthesis and Photophysical and Electrochemical Properties of Pyridine-, Pyrazine- and Triazine-based (D-π-)2A Fluorescent Dyes

Contact Info

Product

Resources

About

Thermochemistry study and improved thermal stability of Yb₁₄MnSb₁₁ alloyed by Ln³⁺ (La–Lu)

Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb₁₄MgSb₁₁

Synthesis and Photophysical and Electrochemical Properties of Pyridine-, Pyrazine- and Triazine-based (D-π-)₂A Fluorescent Dyes