Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks
New coordination compounds of 3<i>d</i>-metals with organic or inorganic frameworks prepared by hydrothermal synthesis are reported herein. The solid-state properties such as magnetism and gas porosity of many of these compounds have been studied. Compounds 1-24 have lattices based on py...
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University of Cambridge
2005
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ndltd-bl.uk-oai-ethos.bl.uk-6047732015-03-20T05:46:45ZHydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworksHumphrey, S. M.2005New coordination compounds of 3<i>d</i>-metals with organic or inorganic frameworks prepared by hydrothermal synthesis are reported herein. The solid-state properties such as magnetism and gas porosity of many of these compounds have been studied. Compounds 1-24 have lattices based on pyridine-2,<i>x</i>-carboxylate ligands (<i>x</i> = 3,4 and 5). Of particular interest are the closely related materials [Co<sub>3</sub>(2,4-pdc)<sub>2</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>].9H<sub>2</sub>O (7a) and [Co<sub>3</sub>(2,4-pdc)<sub>2</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>].7H<sub>2</sub>O (9) that have 1-dimensional channelled frameworks that retain their porosity when guest solvent is removed. Gas sorption studies of 7a suggest a large capacity for H<sub>2</sub> sorption and a high selectivity for that nature of adsorbent. DC susceptibility measurements of the layered bimetallic material [Co<sub>3</sub>Cu<sub>2</sub>(2,4-pdc)<sub>4</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>(OH<sub>2</sub>)<sub>4</sub>] (16) suggest inverse hysteresis-type behaviour. The topological ferrimagnet [Co<sub>3</sub>(2,5-pdc)<sub>2</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>(OH<sub>2</sub>)<sub>2</sub>] (18) has been found to exhibit unusual metamagnetism with multiple areas of bistability. The complex inorganic coordination materials 25-27 are based on lattices of AsO<sub>4</sub><sup>-</sup> and exhibit weak ferromagnetic exchange at low temperature. The novel compounds 28-40 are based on lattices of the hexaanion of mellitic acid; the family of compounds M’<sub>2</sub>[M<sub>2</sub>(mela)(OH<sub>2</sub>)<sub>2</sub>] (M = Mn, Co, Ni; M’ = K, Rb, Cs) (28-31) have been studied by DC magnetometry, while other related structures are also reported. The new materials 41-54 have organothiolate lattices provided by thiosalicylic acid and 2- and 6-mercaptonicotinic. The properties of compounds of Mn<sup>II</sup> formed by <i>in situ</i> redox chemistry and S-S bridge formation (41 and 44) are discussed. Multiple coordination geometries have been observed in the complex materials [Co<sub>4</sub>(2-mna)(OH<sub>2</sub>)] (45) and [Fe<sub>11</sub>(6-mna)<sub>8</sub>)(<i>μ</i><sub>3</sub>-OH)<sub>6</sub>].H<sub>2</sub>O (46), while the unusual magnetism of both species is reported. The first example of a thiolate-containing porous coordination solid [Co<sub>2</sub>(6-mna)<sub>2</sub>].3H<sub>2</sub>O (47) is reported and its gas sorption properties have also been studied.546.3University of Cambridgehttp://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.604773Electronic Thesis or Dissertation |
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546.3 Humphrey, S. M. Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| description |
New coordination compounds of 3<i>d</i>-metals with organic or inorganic frameworks prepared by hydrothermal synthesis are reported herein. The solid-state properties such as magnetism and gas porosity of many of these compounds have been studied. Compounds 1-24 have lattices based on pyridine-2,<i>x</i>-carboxylate ligands (<i>x</i> = 3,4 and 5). Of particular interest are the closely related materials [Co<sub>3</sub>(2,4-pdc)<sub>2</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>].9H<sub>2</sub>O (7a) and [Co<sub>3</sub>(2,4-pdc)<sub>2</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>].7H<sub>2</sub>O (9) that have 1-dimensional channelled frameworks that retain their porosity when guest solvent is removed. Gas sorption studies of 7a suggest a large capacity for H<sub>2</sub> sorption and a high selectivity for that nature of adsorbent. DC susceptibility measurements of the layered bimetallic material [Co<sub>3</sub>Cu<sub>2</sub>(2,4-pdc)<sub>4</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>(OH<sub>2</sub>)<sub>4</sub>] (16) suggest inverse hysteresis-type behaviour. The topological ferrimagnet [Co<sub>3</sub>(2,5-pdc)<sub>2</sub>(<i>μ</i><sub>3</sub>-OH)<sub>2</sub>(OH<sub>2</sub>)<sub>2</sub>] (18) has been found to exhibit unusual metamagnetism with multiple areas of bistability. The complex inorganic coordination materials 25-27 are based on lattices of AsO<sub>4</sub><sup>-</sup> and exhibit weak ferromagnetic exchange at low temperature. The novel compounds 28-40 are based on lattices of the hexaanion of mellitic acid; the family of compounds M’<sub>2</sub>[M<sub>2</sub>(mela)(OH<sub>2</sub>)<sub>2</sub>] (M = Mn, Co, Ni; M’ = K, Rb, Cs) (28-31) have been studied by DC magnetometry, while other related structures are also reported. The new materials 41-54 have organothiolate lattices provided by thiosalicylic acid and 2- and 6-mercaptonicotinic. The properties of compounds of Mn<sup>II</sup> formed by <i>in situ</i> redox chemistry and S-S bridge formation (41 and 44) are discussed. Multiple coordination geometries have been observed in the complex materials [Co<sub>4</sub>(2-mna)(OH<sub>2</sub>)] (45) and [Fe<sub>11</sub>(6-mna)<sub>8</sub>)(<i>μ</i><sub>3</sub>-OH)<sub>6</sub>].H<sub>2</sub>O (46), while the unusual magnetism of both species is reported. The first example of a thiolate-containing porous coordination solid [Co<sub>2</sub>(6-mna)<sub>2</sub>].3H<sub>2</sub>O (47) is reported and its gas sorption properties have also been studied. |
| author |
Humphrey, S. M. |
| author_facet |
Humphrey, S. M. |
| author_sort |
Humphrey, S. M. |
| title |
Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| title_short |
Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| title_full |
Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| title_fullStr |
Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| title_full_unstemmed |
Hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| title_sort |
hydrothermal synthesis of new 3d-metal coordination solids with pyridine dicarboxylate, mellitate, arsenate and organothiolate frameworks |
| publisher |
University of Cambridge |
| publishDate |
2005 |
| url |
http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.604773 |
| work_keys_str_mv |
AT humphreysm hydrothermalsynthesisofnew3dmetalcoordinationsolidswithpyridinedicarboxylatemellitatearsenateandorganothiolateframeworks |
| _version_ |
1716794393191514112 |