The Structure and Luminescent Properties of TlZn(PO3)3

Abiad, Abdelaziz El; Es-Sakhi, B.; Mesnaoui, Mohamed; Maazaz, M.; Belharouak, Ilias; Gravereau, P.; Parent, C.; Wallez, Gilles; Flem, G. Le

doi:10.1006/jssc.2000.8898

Cited by 7 publications

(6 citation statements)

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“…In p‐block cations with an n s 2 n p 0 electronic configuration, lone pairs of electrons may thus play a prominent role in controlling the structures and chemical behavior. In inorganic salts, the lone pair is manifested by a distortion of regular coordination geometries by a substantial elongation of certain bonds, as exemplified in, for example, TlF,3 Tl[CuAsO 4 ], Tl[CuPO 4 ]4 or TlZn(PO 3 ) 3 5. In several organometallic compounds, the stereoactive lone pair is manifested by a “half‐naked” cation, with ligands only coordinating one hemisphere, as observed in the crystal structures of complexes between Tl + and tris(pyrazolyl)borate, where the lone pair occupies the fourth position of a tetrahedron bis(pyrazolyl)phosphinate,6 with an obvious gap in the coordination sphere due to the lone pair, and also in [HB(3‐ p ‐tolylpyrazolyl) 3 Tl] 7.…”

Section: Introductionmentioning

confidence: 99%

Structures of Complexes of Thallium(I) and Functionalized Benzoate Ligands with Pronounced Stereoactivity of the Lone Pair of Electrons and Metal−Phenyl π-Bonding

Kristiansson

2002

Eur. J. Inorg. Chem.

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Four complexes between thallium(I) and functionalized benzoate ligands, namely salicylate, p‐aminosalicylate, 3,4‐dimethoxybenzoate and 3,5‐dimethoxybenzoate have been prepared and their structures determined by X‐ray diffraction. They are all based on dimeric, centrosymmetric Tl2(RCOO)2 units with μ2‐bridging carboxylic groups resulting in Tl···Tl separations of 4.2−4.4 Å. These dimeric units are further linked to form infinite coordination polymers. In catena‐[bis(μ3‐salicylato)dithallium(I)] (1) and catena‐[bis(μ3‐4‐aminosalicylato)dithallium(I)] (2) are adjacent units are held together by secondary Tl−O(hydroxy) interactions resulting in a crystal organization which can be described as stair‐like, infinite one‐dimensional polymers. In catena‐[μ4‐(3,4‐dimethoxybenzoato)thallium(I)] (3) bridges each carboxylic group four thallium(I) cations resulting in infinite two‐dimensional, puckered sheets. Finally, in catena‐[μ3‐(3,5‐dimethoxybenzoato)thallium(I)] (4) each carboxylic unit acts as a μ3‐bridging ligand to give nearly planar, infinite double‐stranded arrays of Tl+ cations. Another characteristic structural motif is the tendency of the thallium ion to only use less than one hemisphere to coordinate ligands. This “half‐nakedness” is due to the stereochemically active inert pair (6s2), which thus plays a prominent role in controlling the structures of these compounds. The Tl+ cations are in approximate pyramidal geometries, with four or five oxygen donor atoms in the basal plane and the stereoactive lone pair occupying the apex position of the pyramid. There are, on the naked side of the metal ions, relatively large spaces in nonpolar environments provided by neighboring phenyl groups. The distances between the planes of the phenyl rings and the Tl+ cation are in the range 3.3−3.5 Å, indicating that Tl+−phenyl η6‐interactions are important in the crystal organization. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Introductionmentioning

confidence: 99%

Structures of Complexes of Thallium(I) and Functionalized Benzoate Ligands with Pronounced Stereoactivity of the Lone Pair of Electrons and Metal−Phenyl π-Bonding

Kristiansson

2002

Eur. J. Inorg. Chem.

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“…Angular ranges for O-P-O (102.7-120.6°) and P-O-P (134.2°) angles are also in a good agreement with those usually found in polyphosphate anions. [25][26][27][28][29][30][31]46 Figure 5 shows the 31 P CP MAS spectra of MPoly at two different sample spinning frequencies, (a) 4 kHz and (b) 12 kHz. A Herzfeld-Berger analysis 47 of the sideband pattern in Figure 6a for the phosphorus PO 3 sites in MPoly results in a chemical shift anisotropy (CSA) of (δ 11 , δ 22 , δ 33 ) ) (78, 17, -172) ( 1 ppm, which is in good agreement with literature data for PO 3 sites in polyphosphate salts.…”

Section: Resultsmentioning

confidence: 99%

“…(the function that was minimized during the restrained refinement is defined in expression 1 of ref ). Distance and angle restraints were obtained by averaging the corresponding quantities in the structures of polyphosphate salts, − MP, MPy, and other compounds with a positively charged (+1) melamine moiety as present in the Cambridge Structural Database . The non-hydrogen atom s.u.…”

Section: Methodsmentioning

confidence: 99%

Structural Analysis of a Melaminium Polyphosphate from X-ray Powder Diffraction and Solid-State NMR Data

Brodski¹,

Peschar²,

Schenk³

et al. 2005

J. Phys. Chem. B

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The crystal structure of the environmentally friendly flame retardant melaminium polyphosphate (MPoly) (2,4,6-triamino-1,3,5-triazinium‚PO 3 ) n was determined by a direct-space global optimization technique from X-ray powder diffraction data. Solid-state NMR was used to corroborate the proposed hydrogen-bonding model and to determine the average degree of polymerization (n > 100). An analysis of the crystal structure of MPoly reveals aspects of molecular geometry and packing that are characteristic for melamine-containing compounds and polyphosphate salts. A comparison of MPoly with the crystal structures of its precursors melaminium orthophosphate (MP) and melaminium dihydrogenpyrophosphate (MPy) provides insight in the mechanism of the endothermic dehydration processes that takes place in the reaction path MP f MPy f MPoly. Solid-state NMR characterization of various samples of the same batch showed inhomogeneities in the MPoly composition. Various quantities of orthophosphates were found, which cannot be assigned to be MP.

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“…2). A comparison can be made with other oxygen compounds of thallium(I), for which active lone pairs are generally found to be 0.4±0.7 A Ê distant from the bearer, with correlatively shorter TlÐO bonds (2.38±2.69 A Ê ; El Abiad et al, 2000;Lafjij et al, 2003), close to the sum of the ionic radii of the Tl 3+ and O 2À ions (2.4 A Ê ; Shannon, 1976). Our results show that -Tl 2 SO 4 is structurally comparable to isotypic Tl 2 CrO 4 (Carter & Margulis, 1972) and Tl 2 SeO 4 (Fa Â bry & Breczewski, 1993).…”

Section: Commentmentioning

confidence: 99%

β-Tl₂SO₄

et al. 2004

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The ambient-temperature form of dithallium sulfate, beta-Tl(2)SO(4), is similar to beta-K(2)SO(4) and is characterized by isolated sulfate tetrahedra and two different thallium sites with coordination numbers 9 and 11. All the atoms, except one O atom, lie on mirror planes. In spite of there being a high concentration of Tl(+) cations, the stereochemical activity of the 6s(2) pairs is low, similar to that of isotypic Tl(2)XO(4) compounds (X = Cr and Se). This behaviour is the consequence of both weak Tl-O bonds and strong X-O bonds, because in a Tl-O-X linkage the electronic cloud of the O(2-) anion is strongly distorted and displaced towards X, resulting in a low negative charge in the face of the Tl atom. Consequently, the Coulombic repulsions between the lone pair and the O(2-) anions are weak. All of the Tl(2)XO(4) compounds exhibit the same open packing of A(+) cations and [XO(4)](2-) anions as their isotypic alkali counterparts.

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The Structure and Luminescent Properties of TlZn(PO3)3

Cited by 7 publications

References 20 publications

Structures of Complexes of Thallium(I) and Functionalized Benzoate Ligands with Pronounced Stereoactivity of the Lone Pair of Electrons and Metal−Phenyl π-Bonding

Structures of Complexes of Thallium(I) and Functionalized Benzoate Ligands with Pronounced Stereoactivity of the Lone Pair of Electrons and Metal−Phenyl π-Bonding

Structural Analysis of a Melaminium Polyphosphate from X-ray Powder Diffraction and Solid-State NMR Data

β-Tl₂SO₄

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The Structure and Luminescent Properties of TlZn(PO3)3

Cited by 7 publications

References 20 publications

Structures of Complexes of Thallium(I) and Functionalized Benzoate Ligands with Pronounced Stereoactivity of the Lone Pair of Electrons and Metal−Phenyl π-Bonding

Structures of Complexes of Thallium(I) and Functionalized Benzoate Ligands with Pronounced Stereoactivity of the Lone Pair of Electrons and Metal−Phenyl π-Bonding

Structural Analysis of a Melaminium Polyphosphate from X-ray Powder Diffraction and Solid-State NMR Data

β-Tl2SO4

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β-Tl₂SO₄