A5RE4X[TO4]4crystal growth and photoluminescence. Hydroflux synthesis of sodium rare earth silicate hydroxides

Latshaw, Allison M.; Chance, W. Michael; Trenor, Nathan M.; Morrison, Gregory; Smith, Mark D.; Yeon, Jeongho; Williams, Derek E.; Loye, Hans‐Conrad zur

doi:10.1039/c5ce00630a

Cited by 14 publications

(18 citation statements)

References 30 publications

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“…This is reminiscent of what has been observed in low-dimensional spin systems with domain formation 41. Similar types of deviation compared to other lanthanides have been observed in other europium-based systems, namely in recently published magnetic studies of Na 5 Eu(SiO 4 ) 4 (OH)11 and NaEuGeO 4 42. It has been suggested that this increase in magnetic susceptibility at lower temperatures can be attributed to the presence of a small amount of Eu 2+ impurity 43.…”

supporting

confidence: 80%

“…The theoretical effective magnetic moment of Nd 3+ , Sm 3+ , and Gd 3+ are 3.62, 1.74, and 7.94 per Ln 3+ ion. Further, θ Similar behavior has been observed in Na 5 Ln(SiO 4 ) 4 (OH)11 and the NaLn 9 (GeO 4 ) 6 O 2 series 40.…”

supporting

confidence: 76%

“…[1][2][3][4] Additionally, lanthanide silicates exhibit high thermal stability, ion exchange properties, and rich structural chemistry owing to great number of possible different coordination environments in lanthanide elements. 5 Crystal growth of these silicates can typically be achieved via hydrothermal [6][7][8][9][10] and flux [11][12][13][14][15] growth techniques. The chemistry of lanthanide-based silicates has been summarized by Wickleder in 2002, 16 and that work identifies several mixed alkali-alkaline earth-rare earth silicates reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

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Hydrothermal synthesis, structure, and property characterization of rare earth silicate compounds: NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd)

Sanjeewa

Fulle

McMillen

et al. 2015

Solid State Sciences

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A series of new lanthanide (Ln) silicates have been synthesized using high temperature hydrothermal techniques, and structurally characterized using single crystal and powder X-ray diffraction. The compounds have the general formula NaBa 3 Ln 3 Si 6 O 20 (Ln = Y, Nd, Sm, Eu, Gd), and crystallize in the space group Ama2 (No.40). As a representative example, the unit cell parameters of NaBa 3 Gd 3 Si 6 O 20 are a = 14.731(3) Å, b = 23.864(5) Å, c = 5.5449(11) Å and Z = 4. The title compounds adopt a three dimensional polar acentric framework made of Ln−O−Si bonding. The framework is comprised of LnO 8 and LnO 7 units forming edge-sharing infinite chains along the c-axis. These oxy-bridged infinite chains are also linked by [Si 4 O 13 ] tetrasilicate and [Si 2 O 7 ] disilicate units to form the three-dimensional framework structure, with Ba 2+ and Na + cations residing inside channels of the framework. The polarity in the structure is imparted by the unusual tetrasilicate arrangement. The luminescence and magnetic properties were investigated on selected compounds. The temperature dependent magnetic susceptibility measurements on the Nd, Sm, and Gd derivatives reveal a Curie-Weiss behavior with an antiferromagnetic coupling parameter. For the Eu-derivative, the temperature dependent magnetic susceptibility deviates significantly from Curie-Weiss behavior. Luminescence properties of NaBa 3 Eu 3 Si 6 O 20 and NaBa 3 Sm 3 Si 6 O 20 compounds exhibited the characteristic transitions of Eu 3+ (5 D 0 → 7 F J , J = 0-4) and Sm 3+ (4 G 5/2 → 6 H J , J = 5/2, 7/2), respectively, leading to strong visible red and orange emissions, respectively.

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supporting

confidence: 80%

supporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

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Hydrothermal synthesis, structure, and property characterization of rare earth silicate compounds: NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd)

Sanjeewa

Fulle

McMillen

et al. 2015

Solid State Sciences

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“…Silicates are an expansive class of extended structures that are based on linked SiO4 tetrahedral building blocks and that encompass many diverse compositions [1][2][3][4][5][6] including numerous examples of complex rare earth containing silicate structures. The presence of rare earth elements in the silicate structure can lead to interesting optical [5,[7][8][9][10] and magnetic [4,[11][12][13][14] properties. Furthermore, a unique feature of the rare earth silicates is the existence of a series of structural analogs and, at times, new structure types when a rare earth cation size limit is reached above or below the point at which a given structure ceases to form.…”

Section: Introductionmentioning

confidence: 99%

“…While each case is unique, one can state that, in general, the rigidity of the crystal structure controls the size range of lanthanides that can be incorporated. Some structures, such as Na5RE4X[SiO4]4 (RE = Pr, Nd, Sm-Yb, Y; X = F, OH), are not very rigid and their rare earth coordination environment site is capable of accommodating a wide range of rare earths extending in size from 0.985 Å (Yb) to 1.126 Å (Pr) [13,15,16]. Other silicate structures that have a more rigid framework structure are often limited to only a small sub-set of rare earths and the structure tends to change when the next sized rare earth falls outside the size range that can be accommodated.…”

Section: Introductionmentioning

confidence: 99%

Influence of rare earth cation size on the crystal structure in rare earth silicates, Na2RESiO4(OH) (RE = Sc, Yb) and NaRESiO4 (RE = La, Yb)

Latshaw

Wilkins

Chance

et al. 2016

Solid State Sciences

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= 5. For n = 2-13, the transition or switch from weak (primarily dipole-dipole-type) inter-monomer interactions to a preference for polar covalent bonding occurs within n = 5-9. Thermodynamic evidence for this transition is provided. The results demonstrate a significant risk associated with crystal structure prediction from the ground up (i.e., based on bonding patterns in small clusters). The path from monomers through extended solids with increasing n is discussed to be associated with transitions in structure and bonding that are not anticipated by the bonding in small clusters. 2O3 with 98% H2SO4 (porcelain crucible, 230 C resp. 210 C, 5 d; cooling to 100 C at a rate of 2 C/h, 89 and 91% yield for the K and Cs compound, resp.). KSb(SO 4 ) 2 crystallizes in the monoclinic space group P2 1 /c (Z = 4, single crystal XRD), and CsSb(SO 4 ) 2 in the orthorhombic space group P2 1 2 1 2 1 (Z = 4). Both compounds show the Sb 3+ cations in a seesaw-type coordination of O atoms from different anions, but exhibit complex 2D and 1D linked anionic structures. The alkali cations are located between the layers or chains. The band gaps are estimated to be 4.64 eV for KSb(SO 4 ) 2 and 4.68 eV for CsSb (SO 4 -Eu 7 Cd 4 Sb 8-x As x (x = 2, 3, 4, and 5) solid solutions are prepared from the elements in a molten Sn flux (alumina crucible in evacuated silica tubes, 1. 600 C, 6 h; 2. 1000 C, 96 h; cooling to 600 C at a rate of 5 C/h). The title phases crystallizes in the I-centered monoclinic space group I2/m (Z = 4, single crystal XRD) and contain parallel double pentagonal tubes resulting from Cd-Pn (Pn: Sb, As) and Pn-Pn bonding. These double pentagons are formed through corner sharing of Cd-centered CdPn 4 tetrahedra and a Pn-Pn interaction of two adjacent CdPn 4 tetrahedra. Theoretical calculations predict that Sb-rich compounds should be metallic or semimetallic and that they should become more insulating as As levels increase. Members of the solid-solution order ferromagnetically between 5 and 6 K and exhibit electrical resistivities ranging from 0.57 (50 K) to 26 m·cm (300 K) which increase with As levels. -Single crystals of Na 2 ScSiO 4 (OH) (I) and Na 2 YbSiO 4 (OH) (II) are prepared by hydrothermal reaction of a 2:1 molar mixture of Na 2 SiO 3 and Sc 2 O 3 (Yb 2 O 3 ) in a NaOH based hydroflux (autoclave, 230 C, 48 h; cooling to 80 C at a rate of 0.1 C/min for (I) or quenching to 25 C). Crystals of NaLaSiO 4 (III) and NaYbSiO 4 (IV) are grown from La 2 O 3 (Yb 2 O 3 ), Na 2 CO 3 , and SiO 2 using a NaF/NaCl eutectic flux (Ag crucible, 900 C, 48 h). Compounds (I) to (II) crystallize in the orthorhombic space group Pca2 1 (Z = 8, single crystal XRD) while the structure of (III) is refined in the orthorhombic space group Pca2 1 (Z = 4) and (IV) in the orthorhombic space group Pnma (Z =4 [CuCl 4 ] crystallizes in the orthorhombic space group P2 1 2 1 2 1 with Z = 8 (single crystal XRD). Its asymmetric unit consists of four unique Et 2 cations and three unique anions. Two of the three Cu atoms adopt a d...

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Ba3Na(OH)3(CO3)2: A Non-centrosymmetric Hydroxycarbonate Crystallized Using the Hydroflux Method

et al. 2018

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A₅RE₄X[TO₄]₄crystal growth and photoluminescence. Hydroflux synthesis of sodium rare earth silicate hydroxides

Cited by 14 publications

References 30 publications

Hydrothermal synthesis, structure, and property characterization of rare earth silicate compounds: NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd)

Hydrothermal synthesis, structure, and property characterization of rare earth silicate compounds: NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd)

Influence of rare earth cation size on the crystal structure in rare earth silicates, Na2RESiO4(OH) (RE = Sc, Yb) and NaRESiO4 (RE = La, Yb)

Ba3Na(OH)3(CO3)2: A Non-centrosymmetric Hydroxycarbonate Crystallized Using the Hydroflux Method

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