Rhodium(III) aqua ion salts of ambivalent self assembled superanion capsules

Alexander Drljaca; Michaele J. Hardie; Timothy J. Ness; Colin L. Raston

doi:10.1002/1099-0682(200010)2000:10<2221::AID-EJIC2221>3.0.CO;2-D

Rhodium(III) aqua ion salts of ambivalent self assembled superanion capsules

Alexander Drljaca, Michaele J. Hardie, Timothy J. Ness, Colin L. Raston

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

42 Citations (Scopus)

Abstract

The self assembled superanionic capsule [{Na⁺subset of(18-crown-6)(OH₂)₂}subset of{(p-sulfonatocalix[4]arene^4-)2}]^7- (X^7-) forms a 1:1 crystalline complex with dinuclear [Rh₂(μ-OH)₂(H₂O)₈]⁴⁺ when the cation is treated with sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2. The overall composition of the crystalline solid is [Rh₂(μ-OH)₂(H₂O)₈][X + 3 H⁺]·11.5H₂O. Treatment of a complex mixture of polynuclear rhodium(III) aqua ions in perchloric acid with excess sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2, results in selective retrieval of the tri- and tetranuclear rhodium(III) species in a single 1:1 co-crystallised phase, isolated as the hydrate salt with overall composition [Rh₃(μ-OH)₄(H₂O)₁₀][Rh₄(μ-OH)₆(H₂O)₁₂][2 X + 3 H⁺][Na(H₂O)(ClO₄)]₂·27H₂O. The tri- and tetranuclear Rh cations both have a cyclic structure with μ-hydroxide and terminal water ligands. Despite the differences in cation charge and size both complexes show the same arrangement of polynuclear cations and superanions although the trimer/tetramer complex shows additional coordination of a second Na centre by the calixarenes. At pH 0.35 the reaction leads to the selective retrieval of the tetranuclear cation in the complex [Rh₄(μ-OH)₆(H₂O)₁₂][X + {X - 2 H₂O} + 8 H⁺]·33H₂O, where a second type of dehydrated superanion is found, where the two sodium bound water molecules have been replaced by O-centres of calixarene sulfonate groups, illustrating the versatile nature of the superanion chemistry.

Original language	English
Pages (from-to)	2221-2229
Number of pages	9
Journal	European Journal of Inorganic Chemistry
Issue number	10
DOIs	https://doi.org/10.1002/1099-0682(200010)2000:10<2221::AID-EJIC2221>3.0.CO;2-D
Publication status	Published - 1 Jan 2000
Externally published	Yes

Keywords

Calixarenes
Capsules
Crown compounds
Rhodium
Supramolecular chemistry

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10.1002/1099-0682(200010)2000:10<2221::AID-EJIC2221>3.0.CO;2-DLicence: In Copyright

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@article{179c14aef4dd43869d023e1ca9e01c69,

title = "Rhodium(III) aqua ion salts of ambivalent self assembled superanion capsules",

abstract = "The self assembled superanionic capsule [{Na+subset of(18-crown-6)(OH2)2}subset of{(p-sulfonatocalix[4]arene4-)2}]7- (X7-) forms a 1:1 crystalline complex with dinuclear [Rh2(μ-OH)2(H2O)8]4+ when the cation is treated with sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2. The overall composition of the crystalline solid is [Rh2(μ-OH)2(H2O)8][X + 3 H+]·11.5H2O. Treatment of a complex mixture of polynuclear rhodium(III) aqua ions in perchloric acid with excess sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2, results in selective retrieval of the tri- and tetranuclear rhodium(III) species in a single 1:1 co-crystallised phase, isolated as the hydrate salt with overall composition [Rh3(μ-OH)4(H2O)10][Rh4(μ-OH)6(H2O)12][2 X + 3 H+][Na(H2O)(ClO4)]2·27H2O. The tri- and tetranuclear Rh cations both have a cyclic structure with μ-hydroxide and terminal water ligands. Despite the differences in cation charge and size both complexes show the same arrangement of polynuclear cations and superanions although the trimer/tetramer complex shows additional coordination of a second Na centre by the calixarenes. At pH 0.35 the reaction leads to the selective retrieval of the tetranuclear cation in the complex [Rh4(μ-OH)6(H2O)12][X + {X - 2 H2O} + 8 H+]·33H2O, where a second type of dehydrated superanion is found, where the two sodium bound water molecules have been replaced by O-centres of calixarene sulfonate groups, illustrating the versatile nature of the superanion chemistry.",

keywords = "Calixarenes, Capsules, Crown compounds, Rhodium, Supramolecular chemistry",

author = "Alexander Drljaca and Hardie, {Michaele J.} and Ness, {Timothy J.} and Raston, {Colin L.}",

year = "2000",

month = jan,

day = "1",

doi = "10.1002/1099-0682(200010)2000:10<2221::AID-EJIC2221>3.0.CO;2-D",

language = "English",

pages = "2221--2229",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

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TY - JOUR

T1 - Rhodium(III) aqua ion salts of ambivalent self assembled superanion capsules

AU - Drljaca, Alexander

AU - Hardie, Michaele J.

AU - Ness, Timothy J.

AU - Raston, Colin L.

PY - 2000/1/1

Y1 - 2000/1/1

N2 - The self assembled superanionic capsule [{Na+subset of(18-crown-6)(OH2)2}subset of{(p-sulfonatocalix[4]arene4-)2}]7- (X7-) forms a 1:1 crystalline complex with dinuclear [Rh2(μ-OH)2(H2O)8]4+ when the cation is treated with sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2. The overall composition of the crystalline solid is [Rh2(μ-OH)2(H2O)8][X + 3 H+]·11.5H2O. Treatment of a complex mixture of polynuclear rhodium(III) aqua ions in perchloric acid with excess sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2, results in selective retrieval of the tri- and tetranuclear rhodium(III) species in a single 1:1 co-crystallised phase, isolated as the hydrate salt with overall composition [Rh3(μ-OH)4(H2O)10][Rh4(μ-OH)6(H2O)12][2 X + 3 H+][Na(H2O)(ClO4)]2·27H2O. The tri- and tetranuclear Rh cations both have a cyclic structure with μ-hydroxide and terminal water ligands. Despite the differences in cation charge and size both complexes show the same arrangement of polynuclear cations and superanions although the trimer/tetramer complex shows additional coordination of a second Na centre by the calixarenes. At pH 0.35 the reaction leads to the selective retrieval of the tetranuclear cation in the complex [Rh4(μ-OH)6(H2O)12][X + {X - 2 H2O} + 8 H+]·33H2O, where a second type of dehydrated superanion is found, where the two sodium bound water molecules have been replaced by O-centres of calixarene sulfonate groups, illustrating the versatile nature of the superanion chemistry.

AB - The self assembled superanionic capsule [{Na+subset of(18-crown-6)(OH2)2}subset of{(p-sulfonatocalix[4]arene4-)2}]7- (X7-) forms a 1:1 crystalline complex with dinuclear [Rh2(μ-OH)2(H2O)8]4+ when the cation is treated with sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2. The overall composition of the crystalline solid is [Rh2(μ-OH)2(H2O)8][X + 3 H+]·11.5H2O. Treatment of a complex mixture of polynuclear rhodium(III) aqua ions in perchloric acid with excess sodium p-sulfonatocalix[4]arene and 18-crown-6 at pH 2, results in selective retrieval of the tri- and tetranuclear rhodium(III) species in a single 1:1 co-crystallised phase, isolated as the hydrate salt with overall composition [Rh3(μ-OH)4(H2O)10][Rh4(μ-OH)6(H2O)12][2 X + 3 H+][Na(H2O)(ClO4)]2·27H2O. The tri- and tetranuclear Rh cations both have a cyclic structure with μ-hydroxide and terminal water ligands. Despite the differences in cation charge and size both complexes show the same arrangement of polynuclear cations and superanions although the trimer/tetramer complex shows additional coordination of a second Na centre by the calixarenes. At pH 0.35 the reaction leads to the selective retrieval of the tetranuclear cation in the complex [Rh4(μ-OH)6(H2O)12][X + {X - 2 H2O} + 8 H+]·33H2O, where a second type of dehydrated superanion is found, where the two sodium bound water molecules have been replaced by O-centres of calixarene sulfonate groups, illustrating the versatile nature of the superanion chemistry.

KW - Calixarenes

KW - Capsules

KW - Crown compounds

KW - Rhodium

KW - Supramolecular chemistry

UR - http://www.scopus.com/inward/record.url?scp=0033781765&partnerID=8YFLogxK

U2 - 10.1002/1099-0682(200010)2000:10<2221::AID-EJIC2221>3.0.CO;2-D

DO - 10.1002/1099-0682(200010)2000:10<2221::AID-EJIC2221>3.0.CO;2-D

M3 - Article

AN - SCOPUS:0033781765

SN - 1434-1948

SP - 2221

EP - 2229

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 10

ER -

Rhodium(III) aqua ion salts of ambivalent self assembled superanion capsules

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Keywords

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