La structure cristalline du tétramétaphosphate de cuivre, Cu2P4O12

Heterovalent Zr4+-Cu2+ substitution in zirconium pyrophosphate: From theoretical models to synthesis and utilization

“…Crystalographically, ZrP 2 O 7 and CuP 2 O 6 phosphates are very different [35,36] and, besides the distinctions in crystal symmetry, the degree of condensation of phosphate groups in these compounds is not the same as well. In pyrophosphate of Zr(IV), PO 4 tetrahedra are linked in couples via P O P connection forming P 2 O 7 groups, while polyphosphate of Cu(II) represents a cyclic tetraphosphate where four PO 4 groups are linked in a ring forming P 4 O 12 groups.…”

Heterovalent Zr4+-Cu2+ substitution in zirconium pyrophosphate: From theoretical models to synthesis and utilization

“…Crystalographically, ZrP 2 O 7 and CuP 2 O 6 phosphates are very different [35,36] and, besides the distinctions in crystal symmetry, the degree of condensation of phosphate groups in these compounds is not the same as well. In pyrophosphate of Zr(IV), PO 4 tetrahedra are linked in couples via P O P connection forming P 2 O 7 groups, while polyphosphate of Cu(II) represents a cyclic tetraphosphate where four PO 4 groups are linked in a ring forming P 4 O 12 groups.…”

Structural characterization and calorimetric dissolution behavior of Na2O CuO P2O5 glasses

“…The presence of Q (1) and Q (3) species may also be due to slight departures of the experimental compositions from the metaphosphate composition, but they are not expected to be present simultaneously, since charge compensation would not be necessary in those cases. Therefore, we conclude that the presence of high CuO contents in meta-phosphates (line II) provokes a partial depolymerization of the phosphate chains, thus creating PO3 end groups compensated by the creation of Q (3) branching groups between chain fragments, thus insuring the reticulation of the glass network and providing new P O terminal sites, probably to accommodate a distorted octahedral environment of oxygen atoms around the Cu 2 + ions [28], [30].…”

“…It is known that the structure of the Na2Cu(PO3)2 crystalline phase corresponding to the glass composition x = 25 is made of infinite metaphosphate chains [28], whereas the crystal with composition Cu(PO3)2 (x = 50) is made of four membered P4O12 cyclic units, i.e. it is more precisely described by the formula Cu2P4O12 [30]. Furthermore, a 31 P MAS-NMR study of this series of glasses has shown that for high Cu contents, the glass contains both -O-PO2-O (denoted as Q (2) ) middle groups and -O-PO3 (denoted as Q (1) ) end groups [16].…”

Facile synthesis of mononuclear early transition-metal complexes of κ 3 cyclo-tetrametaphosphate ([P 4 O 12 ] 4− ) and cyclo-trimetaphosphate ([P 3 O 9 ] 3−

“…34 Complex [PPN] 2 [(P 3 O 9 )Mo(CO) 2 (η 3 -C 3 H 5 )] ( 7) has two characteristic CuO stretches at 1918 and 1812 cm −1 which, as expected, appear at higher energy compared to those of the already reported salt [PPN] 3 [(P 3 O 9 )Mo(CO) 3 ] (6). 38 (10) manifests one signal at 930 cm −1 , characteristic of a VuO stretch (Table S2 †). To the best of our knowledge, there is only one previous report of a fully characterized and stabilized monomeric oxo fluoride vanadium compound, reported by Roesky et al The complex Ph 3 PNVOF 2 was prepared by treating the ligand (Ph 3 PNSiMe 3 ) with the precursor (VOF 3 ) at low temperature (−73 °C) and stirring for twelve hours.…”

Heterovalent Zr4+-Cu2+ substitution in zirconium pyrophosphate: From theoretical models to synthesis and utilization

“…Crystalographically, ZrP 2 O 7 and CuP 2 O 6 phosphates are very different [35,36] and, besides the distinctions in crystal symmetry, the degree of condensation of phosphate groups in these compounds is not the same as well. In pyrophosphate of Zr(IV), PO 4 tetrahedra are linked in couples via P O P connection forming P 2 O 7 groups, while polyphosphate of Cu(II) represents a cyclic tetraphosphate where four PO 4 groups are linked in a ring forming P 4 O 12 groups.…”

Structural characterization and calorimetric dissolution behavior of Na2O CuO P2O5 glasses

“…The presence of Q (1) and Q (3) species may also be due to slight departures of the experimental compositions from the metaphosphate composition, but they are not expected to be present simultaneously, since charge compensation would not be necessary in those cases. Therefore, we conclude that the presence of high CuO contents in meta-phosphates (line II) provokes a partial depolymerization of the phosphate chains, thus creating PO3 end groups compensated by the creation of Q (3) branching groups between chain fragments, thus insuring the reticulation of the glass network and providing new P O terminal sites, probably to accommodate a distorted octahedral environment of oxygen atoms around the Cu 2 + ions [28], [30].…”

“…It is known that the structure of the Na2Cu(PO3)2 crystalline phase corresponding to the glass composition x = 25 is made of infinite metaphosphate chains [28], whereas the crystal with composition Cu(PO3)2 (x = 50) is made of four membered P4O12 cyclic units, i.e. it is more precisely described by the formula Cu2P4O12 [30]. Furthermore, a 31 P MAS-NMR study of this series of glasses has shown that for high Cu contents, the glass contains both -O-PO2-O (denoted as Q (2) ) middle groups and -O-PO3 (denoted as Q (1) ) end groups [16].…”

Facile synthesis of mononuclear early transition-metal complexes of κ 3 cyclo-tetrametaphosphate ([P 4 O 12 ] 4− ) and cyclo-trimetaphosphate ([P 3 O 9 ] 3−

“…34 Complex [PPN] 2 [(P 3 O 9 )Mo(CO) 2 (η 3 -C 3 H 5 )] ( 7) has two characteristic CuO stretches at 1918 and 1812 cm −1 which, as expected, appear at higher energy compared to those of the already reported salt [PPN] 3 [(P 3 O 9 )Mo(CO) 3 ] (6). 38 (10) manifests one signal at 930 cm −1 , characteristic of a VuO stretch (Table S2 †). To the best of our knowledge, there is only one previous report of a fully characterized and stabilized monomeric oxo fluoride vanadium compound, reported by Roesky et al The complex Ph 3 PNVOF 2 was prepared by treating the ligand (Ph 3 PNSiMe 3 ) with the precursor (VOF 3 ) at low temperature (−73 °C) and stirring for twelve hours.…”

Heterovalent Zr4+-Cu2+ substitution in zirconium pyrophosphate: From theoretical models to synthesis and utilization

“…Crystalographically, ZrP 2 O 7 and CuP 2 O 6 phosphates are very different [35,36] and, besides the distinctions in crystal symmetry, the degree of condensation of phosphate groups in these compounds is not the same as well. In pyrophosphate of Zr(IV), PO 4 tetrahedra are linked in couples via P O P connection forming P 2 O 7 groups, while polyphosphate of Cu(II) represents a cyclic tetraphosphate where four PO 4 groups are linked in a ring forming P 4 O 12 groups.…”

Structural characterization and calorimetric dissolution behavior of Na2O CuO P2O5 glasses

“…The presence of Q (1) and Q (3) species may also be due to slight departures of the experimental compositions from the metaphosphate composition, but they are not expected to be present simultaneously, since charge compensation would not be necessary in those cases. Therefore, we conclude that the presence of high CuO contents in meta-phosphates (line II) provokes a partial depolymerization of the phosphate chains, thus creating PO3 end groups compensated by the creation of Q (3) branching groups between chain fragments, thus insuring the reticulation of the glass network and providing new P O terminal sites, probably to accommodate a distorted octahedral environment of oxygen atoms around the Cu 2 + ions [28], [30].…”

“…It is known that the structure of the Na2Cu(PO3)2 crystalline phase corresponding to the glass composition x = 25 is made of infinite metaphosphate chains [28], whereas the crystal with composition Cu(PO3)2 (x = 50) is made of four membered P4O12 cyclic units, i.e. it is more precisely described by the formula Cu2P4O12 [30]. Furthermore, a 31 P MAS-NMR study of this series of glasses has shown that for high Cu contents, the glass contains both -O-PO2-O (denoted as Q (2) ) middle groups and -O-PO3 (denoted as Q (1) ) end groups [16].…”

Facile synthesis of mononuclear early transition-metal complexes of κ 3 cyclo-tetrametaphosphate ([P 4 O 12 ] 4− ) and cyclo-trimetaphosphate ([P 3 O 9 ] 3−

“…34 Complex [PPN] 2 [(P 3 O 9 )Mo(CO) 2 (η 3 -C 3 H 5 )] ( 7) has two characteristic CuO stretches at 1918 and 1812 cm −1 which, as expected, appear at higher energy compared to those of the already reported salt [PPN] 3 [(P 3 O 9 )Mo(CO) 3 ] (6). 38 (10) manifests one signal at 930 cm −1 , characteristic of a VuO stretch (Table S2 †). To the best of our knowledge, there is only one previous report of a fully characterized and stabilized monomeric oxo fluoride vanadium compound, reported by Roesky et al The complex Ph 3 PNVOF 2 was prepared by treating the ligand (Ph 3 PNSiMe 3 ) with the precursor (VOF 3 ) at low temperature (−73 °C) and stirring for twelve hours.…”