Abstract
31P solid-state nuclear magnetic resonance (NMR) spectra of 12 metal-containing selenophosphates have been examined to distinguish between the [P2Se6]4-, [PSe4]3-, [P4Se10]4-, [P2Se7]4-, and [P2Se9]4- anions. There is a general correlation between the chemical shifts (CSs) of anions and the presence of a P-P bond. The [P2Se6]4- and [P4Se10]4- anions both contain a P-P bond and resonate between 25 and 95 ppm whereas the [PSe4]3-, [P2Se7]4-, and [P2Se9]4- anions do not contain a P-P bond and resonate between -115 and -30 ppm. The chemical shift anisotropies (CSAs) of compounds containing [PSe4]3- anions are less than 80 ppm, which is significantly smaller than the CSAs of any of the other anions (range: 135-275 ppm). The smaller CSAs of the [PSe4]3- anion are likely due to the unique local tetrahedral symmetry of this anion. Spin-lattice relaxation times (T1) have been determined for the solid compounds and vary between 20 and 3000 s. Unlike the CS, T1 does not appear to correlate with P-P bonding. 31P NMR is also shown to be a good method for impurity detection and identification in the solid compounds. The results of this study suggest that 31P NMR will be a useful tool for anion identification and quantitation in high-temperature melts.
| Original language | English |
|---|---|
| Pages (from-to) | 3399-3405 |
| Number of pages | 7 |
| Journal | Inorganic Chemistry |
| Volume | 42 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Jun 2 2003 |
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- Inorganic Chemistry
Cite this
31P solid state NMR studies of metal selenophosphates containing [P2Se6]4-, [P4Se10]4-, [PSe4]3-, [P2Se7]4-, and [P2Se9]4- ligands. / Canlas, Christian G.; Kanatzidis, Mercouri G; Weliky, David P.
In: Inorganic Chemistry, Vol. 42, No. 11, 02.06.2003, p. 3399-3405.Research output: Contribution to journal › Article
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TY - JOUR
T1 - 31P solid state NMR studies of metal selenophosphates containing [P2Se6]4-, [P4Se10]4-, [PSe4]3-, [P2Se7]4-, and [P2Se9]4- ligands
AU - Canlas, Christian G.
AU - Kanatzidis, Mercouri G
AU - Weliky, David P.
PY - 2003/6/2
Y1 - 2003/6/2
N2 - 31P solid-state nuclear magnetic resonance (NMR) spectra of 12 metal-containing selenophosphates have been examined to distinguish between the [P2Se6]4-, [PSe4]3-, [P4Se10]4-, [P2Se7]4-, and [P2Se9]4- anions. There is a general correlation between the chemical shifts (CSs) of anions and the presence of a P-P bond. The [P2Se6]4- and [P4Se10]4- anions both contain a P-P bond and resonate between 25 and 95 ppm whereas the [PSe4]3-, [P2Se7]4-, and [P2Se9]4- anions do not contain a P-P bond and resonate between -115 and -30 ppm. The chemical shift anisotropies (CSAs) of compounds containing [PSe4]3- anions are less than 80 ppm, which is significantly smaller than the CSAs of any of the other anions (range: 135-275 ppm). The smaller CSAs of the [PSe4]3- anion are likely due to the unique local tetrahedral symmetry of this anion. Spin-lattice relaxation times (T1) have been determined for the solid compounds and vary between 20 and 3000 s. Unlike the CS, T1 does not appear to correlate with P-P bonding. 31P NMR is also shown to be a good method for impurity detection and identification in the solid compounds. The results of this study suggest that 31P NMR will be a useful tool for anion identification and quantitation in high-temperature melts.
AB - 31P solid-state nuclear magnetic resonance (NMR) spectra of 12 metal-containing selenophosphates have been examined to distinguish between the [P2Se6]4-, [PSe4]3-, [P4Se10]4-, [P2Se7]4-, and [P2Se9]4- anions. There is a general correlation between the chemical shifts (CSs) of anions and the presence of a P-P bond. The [P2Se6]4- and [P4Se10]4- anions both contain a P-P bond and resonate between 25 and 95 ppm whereas the [PSe4]3-, [P2Se7]4-, and [P2Se9]4- anions do not contain a P-P bond and resonate between -115 and -30 ppm. The chemical shift anisotropies (CSAs) of compounds containing [PSe4]3- anions are less than 80 ppm, which is significantly smaller than the CSAs of any of the other anions (range: 135-275 ppm). The smaller CSAs of the [PSe4]3- anion are likely due to the unique local tetrahedral symmetry of this anion. Spin-lattice relaxation times (T1) have been determined for the solid compounds and vary between 20 and 3000 s. Unlike the CS, T1 does not appear to correlate with P-P bonding. 31P NMR is also shown to be a good method for impurity detection and identification in the solid compounds. The results of this study suggest that 31P NMR will be a useful tool for anion identification and quantitation in high-temperature melts.
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U2 - 10.1021/ic025946j
DO - 10.1021/ic025946j
M3 - Article
VL - 42
SP - 3399
EP - 3405
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 11
ER -