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Title: Retention of structural cores in the synthesis of high-nuclearity polyoxoalkoxomolybdate clusters encapsulating [Na(H{sub 2}O){sub 3}]{sup +} and [MoO{sub 3}] moieties. Hydrothermal syntheses and structures of (NH{sub 4}){sub 7}[NaH{sub 12}Mo{sub 16}O{sub 52}]{center_dot}4H{sub 2}O and (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 14}Mo{sub 16}O{sub 52}]{center_dot}8H{sub 2}O and their structural relationships to the class of superclusters [XH{sub n}Mo{sub 42}O{sub 109}((OCH{sub 2}){sub 3}CR){sub 7}]{sup m{minus}} (X = Na(H{sub 2}O){sub 3}{sup +}: n=13, m=9; n=15, m=7. X = MoO{sub 3}: n = 14, m=9; n=13, m=10)

Abstract

Hydrothermal reactions of molybdenum-oxide precursors with polyalcohols in the presence of base yielded two series of mixed-valence oxomolybdenum clusters, the hexadecanuclear species [XH{sub 12}(Mo{sup VI}O{sub 3}){sub 4}Mo{sup V}{sub 12}O{sub 40}]{sup m{minus}}(X=Na{sup +}, m=7; X=2H{sup +}, m=6) and the superclusters [XH{sub n}Mo{sup VI}{sub 6}Mo{sup V}{sub 36}O{sub 109}(OCH{sub 2}){sub 3}CR{sub 7}]{sup m{minus}} (X=Na-(H{sub 2}O){sub 3}{sup +}, m=9, n=13; X=Na(H{sub 2}O){sub 3}{sup +}, m=7, n=15; X=MoO{sub 3}, m=9, n=14; X=MoO{sub 3}, m=10, n=13). In a representative synthesis for the hexadencanuclear class of materials, the hydrothermal reaction of a mixture of Na{sub 2}MoO{sub 4}{center_dot}2H{sub 2}O, MoO{sub 3}, Mo metal, and NH{sub 4}Cl produced (NH{sub 4}){sub 7}[NaMo{sub 16}(OH){sub 12}O{sub 40}]{center_dot}4h{sub 2}O (1{center_dot}4H{sub 2}O) as red-orange crystals. The compound (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 2}Mo{sub 16}(OH){sub 40}]{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O) was prepared in a similar fashion. The structure of the anion of 1 consists of an {epsilon}-Keggin core H{sub 12}Mo{sub 12}O{sub 40}, capped on four hexagonal faces by MoO{sub 3} units and encapsulating a Na{sup +} cation. The structure of the oxomolybdenum framework of 2 is essentially identical to that of 1; however, the central cavity is now occupied by 2H{sup +}.

Authors:
; ;  [1]; ;  [2]
  1. Syracuse Univ., NY (United States)
  2. Univ. of New Orleans, LA (United States)
Publication Date:
OSTI Identifier:
264064
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 35; Journal Issue: 7; Other Information: PBD: 27 Mar 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; MOLYBDATES; CHEMICAL PREPARATION; HYDROTHERMAL SYNTHESIS; CRYSTAL STRUCTURE; ANIONS; ATOMIC CLUSTERS

Citation Formats

Khan, M.I., Chen, Q., Salta, J., O`Connor, C.J., and Zubieta, J. Retention of structural cores in the synthesis of high-nuclearity polyoxoalkoxomolybdate clusters encapsulating [Na(H{sub 2}O){sub 3}]{sup +} and [MoO{sub 3}] moieties. Hydrothermal syntheses and structures of (NH{sub 4}){sub 7}[NaH{sub 12}Mo{sub 16}O{sub 52}]{center_dot}4H{sub 2}O and (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 14}Mo{sub 16}O{sub 52}]{center_dot}8H{sub 2}O and their structural relationships to the class of superclusters [XH{sub n}Mo{sub 42}O{sub 109}((OCH{sub 2}){sub 3}CR){sub 7}]{sup m{minus}} (X = Na(H{sub 2}O){sub 3}{sup +}: n=13, m=9; n=15, m=7. X = MoO{sub 3}: n = 14, m=9; n=13, m=10). United States: N. p., 1996. Web. doi:10.1021/ic9508841.
Khan, M.I., Chen, Q., Salta, J., O`Connor, C.J., & Zubieta, J. Retention of structural cores in the synthesis of high-nuclearity polyoxoalkoxomolybdate clusters encapsulating [Na(H{sub 2}O){sub 3}]{sup +} and [MoO{sub 3}] moieties. Hydrothermal syntheses and structures of (NH{sub 4}){sub 7}[NaH{sub 12}Mo{sub 16}O{sub 52}]{center_dot}4H{sub 2}O and (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 14}Mo{sub 16}O{sub 52}]{center_dot}8H{sub 2}O and their structural relationships to the class of superclusters [XH{sub n}Mo{sub 42}O{sub 109}((OCH{sub 2}){sub 3}CR){sub 7}]{sup m{minus}} (X = Na(H{sub 2}O){sub 3}{sup +}: n=13, m=9; n=15, m=7. X = MoO{sub 3}: n = 14, m=9; n=13, m=10). United States. doi:10.1021/ic9508841.
Khan, M.I., Chen, Q., Salta, J., O`Connor, C.J., and Zubieta, J. Wed . "Retention of structural cores in the synthesis of high-nuclearity polyoxoalkoxomolybdate clusters encapsulating [Na(H{sub 2}O){sub 3}]{sup +} and [MoO{sub 3}] moieties. Hydrothermal syntheses and structures of (NH{sub 4}){sub 7}[NaH{sub 12}Mo{sub 16}O{sub 52}]{center_dot}4H{sub 2}O and (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 14}Mo{sub 16}O{sub 52}]{center_dot}8H{sub 2}O and their structural relationships to the class of superclusters [XH{sub n}Mo{sub 42}O{sub 109}((OCH{sub 2}){sub 3}CR){sub 7}]{sup m{minus}} (X = Na(H{sub 2}O){sub 3}{sup +}: n=13, m=9; n=15, m=7. X = MoO{sub 3}: n = 14, m=9; n=13, m=10)". United States. doi:10.1021/ic9508841.
@article{osti_264064,
title = {Retention of structural cores in the synthesis of high-nuclearity polyoxoalkoxomolybdate clusters encapsulating [Na(H{sub 2}O){sub 3}]{sup +} and [MoO{sub 3}] moieties. Hydrothermal syntheses and structures of (NH{sub 4}){sub 7}[NaH{sub 12}Mo{sub 16}O{sub 52}]{center_dot}4H{sub 2}O and (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 14}Mo{sub 16}O{sub 52}]{center_dot}8H{sub 2}O and their structural relationships to the class of superclusters [XH{sub n}Mo{sub 42}O{sub 109}((OCH{sub 2}){sub 3}CR){sub 7}]{sup m{minus}} (X = Na(H{sub 2}O){sub 3}{sup +}: n=13, m=9; n=15, m=7. X = MoO{sub 3}: n = 14, m=9; n=13, m=10)},
author = {Khan, M.I. and Chen, Q. and Salta, J. and O`Connor, C.J. and Zubieta, J.},
abstractNote = {Hydrothermal reactions of molybdenum-oxide precursors with polyalcohols in the presence of base yielded two series of mixed-valence oxomolybdenum clusters, the hexadecanuclear species [XH{sub 12}(Mo{sup VI}O{sub 3}){sub 4}Mo{sup V}{sub 12}O{sub 40}]{sup m{minus}}(X=Na{sup +}, m=7; X=2H{sup +}, m=6) and the superclusters [XH{sub n}Mo{sup VI}{sub 6}Mo{sup V}{sub 36}O{sub 109}(OCH{sub 2}){sub 3}CR{sub 7}]{sup m{minus}} (X=Na-(H{sub 2}O){sub 3}{sup +}, m=9, n=13; X=Na(H{sub 2}O){sub 3}{sup +}, m=7, n=15; X=MoO{sub 3}, m=9, n=14; X=MoO{sub 3}, m=10, n=13). In a representative synthesis for the hexadencanuclear class of materials, the hydrothermal reaction of a mixture of Na{sub 2}MoO{sub 4}{center_dot}2H{sub 2}O, MoO{sub 3}, Mo metal, and NH{sub 4}Cl produced (NH{sub 4}){sub 7}[NaMo{sub 16}(OH){sub 12}O{sub 40}]{center_dot}4h{sub 2}O (1{center_dot}4H{sub 2}O) as red-orange crystals. The compound (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 2}Mo{sub 16}(OH){sub 40}]{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O) was prepared in a similar fashion. The structure of the anion of 1 consists of an {epsilon}-Keggin core H{sub 12}Mo{sub 12}O{sub 40}, capped on four hexagonal faces by MoO{sub 3} units and encapsulating a Na{sup +} cation. The structure of the oxomolybdenum framework of 2 is essentially identical to that of 1; however, the central cavity is now occupied by 2H{sup +}.},
doi = {10.1021/ic9508841},
journal = {Inorganic Chemistry},
number = 7,
volume = 35,
place = {United States},
year = {1996},
month = {3}
}