Grafting ligands to direct the self-assembly of Co/Ni2+ substituted polyoxometalate clusters

Chris Ritchie; Thomas Boyd; De Liang Long; Evert Ditzel; Leroy Cronin

doi:10.1039/b814076f

Grafting ligands to direct the self-assembly of Co/Ni²⁺ substituted polyoxometalate clusters

Chris Ritchie, Thomas Boyd, De Liang Long, Evert Ditzel, Leroy Cronin

Research output: Contribution to journal › Article › Research › peer-review

32 Citations (Scopus)

Abstract

Four transition metal incorporated phosphotungstates have been synthesized through the reaction of Na₂WO₄, H₃PO₄, Co/Ni(NO₃)₂, and the multifunctional amine N,N′-Bis(2-hydroxyethyl) piperazine (bhep). Na₂(MHbhep(H₂O)₄)[PW₁₀M₂O₃₈(Hbhep)₂] M = Co²⁺ (1), and Ni²⁺(2) represent rare examples of complete transition metal chelate encapsulation within a Keggin polyanion. Slight modification of the reaction procedure yielding 1 also yields the two dimensional material (H₂bhep)₃Na₄[Co₄(H₂O)₂(PW₉O₃₄)₂].15H₂O (3). Finally, the isolation of a phosphotungstate cluster containing 18 Co²⁺ ions is achieved through the bridging of two [Co₉(OH)₃(H₂O)₆(HPO₄)₂(B-α-PW₉O₃₄)₃]¹⁶⁻ clusters by the bhep ligand to form the [(Co₉(OH)₃(H₂O)₃(HPO₄)₂(B-α-PW₉O₃₄)₃)₂ (C₈H₁₈N₂O₂)₃]³²⁻ dimer (4). The dimerisation process is achieved via the monodentate coordination of the hydroxyl groups from three bhep ligands to each polyanion by displacing the water ligands typically found coordinated to the (Co₉) core forming a nanoscale cylinder-like capsule capped by two (Co₉P₅W₂₇) with three BHEP-based ligand spacers.

Original language	English
Pages (from-to)	1587-1592
Number of pages	6
Journal	Dalton Transactions
Issue number	9
DOIs	https://doi.org/10.1039/b814076f
Publication status	Published - 18 Feb 2009
Externally published	Yes

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title = "Grafting ligands to direct the self-assembly of Co/Ni2+ substituted polyoxometalate clusters",

abstract = "Four transition metal incorporated phosphotungstates have been synthesized through the reaction of Na2WO4, H3PO4, Co/Ni(NO3)2, and the multifunctional amine N,N′-Bis(2-hydroxyethyl) piperazine (bhep). Na2(MHbhep(H2O)4)[PW10M2O38(Hbhep)2] M = Co2+ (1), and Ni2+(2) represent rare examples of complete transition metal chelate encapsulation within a Keggin polyanion. Slight modification of the reaction procedure yielding 1 also yields the two dimensional material (H2bhep)3Na4[Co4(H2O)2(PW9O34)2].15H2O (3). Finally, the isolation of a phosphotungstate cluster containing 18 Co2+ ions is achieved through the bridging of two [Co9(OH)3(H2O)6(HPO4)2(B-α-PW9O34)3]16− clusters by the bhep ligand to form the [(Co9(OH)3(H2O)3(HPO4)2(B-α-PW9O34)3)2 (C8H18N2O2)3]32− dimer (4). The dimerisation process is achieved via the monodentate coordination of the hydroxyl groups from three bhep ligands to each polyanion by displacing the water ligands typically found coordinated to the (Co9) core forming a nanoscale cylinder-like capsule capped by two (Co9P5W27) with three BHEP-based ligand spacers.",

author = "Chris Ritchie and Thomas Boyd and Long, {De Liang} and Evert Ditzel and Leroy Cronin",

year = "2009",

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doi = "10.1039/b814076f",

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T1 - Grafting ligands to direct the self-assembly of Co/Ni2+ substituted polyoxometalate clusters

AU - Ritchie, Chris

AU - Boyd, Thomas

AU - Long, De Liang

AU - Ditzel, Evert

AU - Cronin, Leroy

PY - 2009/2/18

Y1 - 2009/2/18

N2 - Four transition metal incorporated phosphotungstates have been synthesized through the reaction of Na2WO4, H3PO4, Co/Ni(NO3)2, and the multifunctional amine N,N′-Bis(2-hydroxyethyl) piperazine (bhep). Na2(MHbhep(H2O)4)[PW10M2O38(Hbhep)2] M = Co2+ (1), and Ni2+(2) represent rare examples of complete transition metal chelate encapsulation within a Keggin polyanion. Slight modification of the reaction procedure yielding 1 also yields the two dimensional material (H2bhep)3Na4[Co4(H2O)2(PW9O34)2].15H2O (3). Finally, the isolation of a phosphotungstate cluster containing 18 Co2+ ions is achieved through the bridging of two [Co9(OH)3(H2O)6(HPO4)2(B-α-PW9O34)3]16− clusters by the bhep ligand to form the [(Co9(OH)3(H2O)3(HPO4)2(B-α-PW9O34)3)2 (C8H18N2O2)3]32− dimer (4). The dimerisation process is achieved via the monodentate coordination of the hydroxyl groups from three bhep ligands to each polyanion by displacing the water ligands typically found coordinated to the (Co9) core forming a nanoscale cylinder-like capsule capped by two (Co9P5W27) with three BHEP-based ligand spacers.

AB - Four transition metal incorporated phosphotungstates have been synthesized through the reaction of Na2WO4, H3PO4, Co/Ni(NO3)2, and the multifunctional amine N,N′-Bis(2-hydroxyethyl) piperazine (bhep). Na2(MHbhep(H2O)4)[PW10M2O38(Hbhep)2] M = Co2+ (1), and Ni2+(2) represent rare examples of complete transition metal chelate encapsulation within a Keggin polyanion. Slight modification of the reaction procedure yielding 1 also yields the two dimensional material (H2bhep)3Na4[Co4(H2O)2(PW9O34)2].15H2O (3). Finally, the isolation of a phosphotungstate cluster containing 18 Co2+ ions is achieved through the bridging of two [Co9(OH)3(H2O)6(HPO4)2(B-α-PW9O34)3]16− clusters by the bhep ligand to form the [(Co9(OH)3(H2O)3(HPO4)2(B-α-PW9O34)3)2 (C8H18N2O2)3]32− dimer (4). The dimerisation process is achieved via the monodentate coordination of the hydroxyl groups from three bhep ligands to each polyanion by displacing the water ligands typically found coordinated to the (Co9) core forming a nanoscale cylinder-like capsule capped by two (Co9P5W27) with three BHEP-based ligand spacers.

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DO - 10.1039/b814076f

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 9

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Grafting ligands to direct the self-assembly of Co/Ni2+ substituted polyoxometalate clusters

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Grafting ligands to direct the self-assembly of Co/Ni²⁺ substituted polyoxometalate clusters