A new phenylene-linked multitopic family of bis(pyrazolyl)methane ligands, (C6H6-n[CH2OCH2CH(pz)2]2)n, where pz is a pyrazolyl ring, has been synthesized by the general reaction of (pz)2CHCH2OH with NaH, followed by the addition of C6H6-n[CH2Br]n. The silver(I) complexes of ligand o-C6H4[CH2OCH2CH(pz)2]2 form coordination polymer. The two other ditopic ligands, which have meta- and para-oriented \"arms\" (-CH2OCH2CH(pz)2), were treated with Ag(I) salts and recrystallized from acetone or acetonitrile to give nine silver(I) complexes, in which the four pyrazolyl rings of the ligand chelate a single silver(I) cation in a distorted tetrahedral environment forming unusually sized mononuclear metallacycles. The silver(I) complexes of the tetratopic and hexatopic ligands form double, mononuclear metallacycles, a new structural form. In the silver complexes of the tetratopic ligand, the double, mononuclear metallacycles are formed by two pairs of para-oriented arms chelating two silver ions on opposite sides of the central arene ring. The silver complexes of the hexatopic ligand also form double, mononuclear metallacycles; however, one metallacycle is formed by para-oriented arms and the other metallacycle is formed by meta-oriented arms. The remaining two arms link these metallacyles into coordination polymers.
The more rigid, ditopic, bis(pyrazolyl)methane ligand m-[CH(pz)2]2C6H4, Lm, yields the monofluoride bridged, binuclear [M2(μ-F)(μ-Lm)2](BF4)3 complexes when treated with M(BF4)2*xH2O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of Lm with Ni(BF4)2*6H2O yields dibridged [Ni2(μ-F)2(μ-Lm)2](BF4)2. The solid state structures
of seven [M2(μ-F)(μ-Lm)2](BF4)3 complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe2(μ-F)(μ-Lm)2](BF4)3 and [Co2(μ-F)(μ-Lm)2](BF4)3complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with J values of -10.4 and -0.67 cm-1, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu2(μ-F)(μ-Lm)2](BF4)3 are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm-1 or more negative.
Because of unusually large J value in [Cu2(μ-F)(μ-Lm)2](BF4)3, the complexes [Cu2(μ-Cl)(μ-Lm)2](BF4)3, [Cu2(μ-Cl)(μ-Lm)2](ClO4)3, [Cu2(μ-OH)(μ-Lm)2](ClO4)3, and [Cu2(μ-Br)(μ-Lm)2](BF4)3 were synthesized. The solid state structures of the [Cu2(μ-Cl)(μ-Lm)2]3+ complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu2(μ-OH)(μ-Lm)2]3+ complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.
nylene-linked multitopic family of bis(pyrazolyl)methane ligands, m-[CH(pz)2]2C6H4, Lm, yields the monofluoride bridged, binuclear [M2(μ-F)(μ-Lm)2](BF4)3 complexes when treated with M(BF4)2*xH2O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of Lm with Ni(BF4)2*6H2O yields dibridged [Ni2(μ-F)2(μ-Lm)2](BF4)2. The solid state structuresof seven [M2(μ-F)(μ-Lm)2](BF4)3 complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe2(μ-F)(μ-Lm)2](BF4)3 and [Co2(μ-F)(μ-Lm)2](BF4)3complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with J values of -10.4 and -0.67 cm-1, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu2(μ-F)(μ-Lm)2](BF4)3 are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm-1 or more negative.
Because of unusually large J value in [Cu2(μ-F)(μ-Lm)2](BF4)3, the complexes [Cu2(μ-Cl)(μ-Lm)2](BF4)3, [Cu2(μ-Cl)(μ-Lm)2](ClO4)3, [Cu2(μ-OH)(μ-Lm)2](ClO4)3, and [Cu2(μ-Br)(μ-Lm)2](BF4)3 were synthesized. The solid state structures of the [Cu2(μ-Cl)(μ-Lm)2]3+ complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu2(μ-OH)(μ-Lm)2]3+ complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.
","abstract_html":"<p>A new phenylene-linked multitopic family of bis(pyrazolyl)methane ligands, (C<sub>6</sub>H<sub>6-n</sub>[CH<sub>2</sub>OCH<sub>2</sub>CH(pz)<sub>2</sub>]<sub>2</sub>)<sub>n</sub>, where pz is a pyrazolyl ring, has been synthesized by the general reaction of (pz)<sub>2</sub>CHCH<sub>2</sub>OH with NaH, followed by the addition of C<sub>6</sub>H<sub>6-n</sub>[CH<sub>2</sub>Br]<sub>n</sub>. The silver(I) complexes of ligand <em>o</em>-C<sub>6</sub>H<sub>4</sub>[CH<sub>2</sub>OCH<sub>2</sub>CH(pz)<sub>2</sub>]<sub>2</sub> form coordination polymer. The two other ditopic ligands, which have meta- and para-oriented "arms" (-CH<sub>2</sub>OCH<sub>2</sub>CH(pz)<sub>2</sub>), were treated with Ag(I) salts and recrystallized from acetone or acetonitrile to give nine silver(I) complexes, in which the four pyrazolyl rings of the ligand chelate a single silver(I) cation in a distorted tetrahedral environment forming unusually sized mononuclear metallacycles. The silver(I) complexes of the tetratopic and hexatopic ligands form double, mononuclear metallacycles, a new structural form. In the silver complexes of the tetratopic ligand, the double, mononuclear metallacycles are formed by two pairs of <em>para</em>-oriented arms chelating two silver ions on opposite sides of the central arene ring. The silver complexes of the hexatopic ligand also form double, mononuclear metallacycles; however, one metallacycle is formed by <em>para</em>-oriented arms and the other metallacycle is formed by <em>meta</em>-oriented arms. The remaining two arms link these metallacyles into coordination polymers.</p><p>The more rigid, ditopic, bis(pyrazolyl)methane ligand <em>m</em>-[CH(pz)<sub>2</sub>]<sub>2</sub>C<sub>6</sub>H<sub>4</sub>, <strong>Lm</strong>, yields the monofluoride bridged, binuclear [M<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> complexes when treated with M(BF<sub>4</sub>)<sub>2</sub>*xH<sub>2</sub>O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of <strong>Lm</strong> with Ni(BF<sub>4</sub>)<sub>2</sub>*6H<sub>2</sub>O yields dibridged [Ni<sub>2</sub>(μ-F)<sub>2</sub>(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>2</sub>. The solid state structures</p> <p>of seven [M<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> and [Co<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub>complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with <em>J</em> values of -10.4 and -0.67 cm<sup>-1</sup>, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm<sup>-1</sup> or more negative.</p> <p>Because of unusually large <em>J</em> value in [Cu<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub>, the complexes [Cu<sub>2</sub>(μ-Cl)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub>, [Cu<sub>2</sub>(μ-Cl)(μ-<strong>Lm</strong>)<sub>2</sub>](ClO<sub>4</sub>)<sub>3</sub>, [Cu<sub>2</sub>(μ-OH)(μ-<strong>Lm</strong>)<sub>2</sub>](ClO<sub>4</sub>)<sub>3</sub>, and [Cu<sub>2</sub>(μ-Br)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> were synthesized. The solid state structures of the [Cu<sub>2</sub>(μ-Cl)(μ-<strong>Lm</strong>)<sub>2</sub>]<sup>3+</sup> complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu<sub>2</sub>(μ-OH)(μ-<strong>Lm</strong>)<sub>2</sub>]<sup>3+</sup> complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.</p>nylene-linked multitopic family of bis(pyrazolyl)methane ligands, <em>m</em>-[CH(pz)<sub>2</sub>]<sub>2</sub>C<sub>6</sub>H<sub>4</sub>, <strong>Lm</strong>, yields the monofluoride bridged, binuclear [M<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> complexes when treated with M(BF<sub>4</sub>)<sub>2</sub>*xH<sub>2</sub>O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of <strong>Lm</strong> with Ni(BF<sub>4</sub>)<sub>2</sub>*6H<sub>2</sub>O yields dibridged [Ni<sub>2</sub>(μ-F)<sub>2</sub>(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>2</sub>. The solid state structures</p> <p>of seven [M<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> and [Co<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub>complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with <em>J</em> values of -10.4 and -0.67 cm<sup>-1</sup>, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm<sup>-1</sup> or more negative.</p> <p>Because of unusually large <em>J</em> value in [Cu<sub>2</sub>(μ-F)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub>, the complexes [Cu<sub>2</sub>(μ-Cl)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub>, [Cu<sub>2</sub>(μ-Cl)(μ-<strong>Lm</strong>)<sub>2</sub>](ClO<sub>4</sub>)<sub>3</sub>, [Cu<sub>2</sub>(μ-OH)(μ-<strong>Lm</strong>)<sub>2</sub>](ClO<sub>4</sub>)<sub>3</sub>, and [Cu<sub>2</sub>(μ-Br)(μ-<strong>Lm</strong>)<sub>2</sub>](BF<sub>4</sub>)<sub>3</sub> were synthesized. The solid state structures of the [Cu<sub>2</sub>(μ-Cl)(μ-<strong>Lm</strong>)<sub>2</sub>]<sup>3+</sup> complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu<sub>2</sub>(μ-OH)(μ-<strong>Lm</strong>)<sub>2</sub>]<sup>3+</sup> complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.</p>","abstract_has_math":false,"creators":["Foley, Elizabeth Ann"],"institution":null,"degree_name":"PhD","degree_level":"Campus Access Dissertation","degree_discipline":"Chemistry and Biochemistry","degree_department":null,"school":null,"contributors":["Daniel L. Reger"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-01-01T08:00:00Z","date_published":"2009-01-01T08:00:00Z","updated_at":"2026-07-24T04:36:43Z","subjects":["Chemistry","Physical Sciences and Mathematics"],"languages":[],"rights":["© 2009, Elizabeth Ann Foley"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholarcommons.sc.edu/etd/28","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Daniel L. Reger"]},{"key":"dc:creator","label":"Author","values":["Foley, Elizabeth Ann"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry and Biochemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Campus Access Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["PhD"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Physical Sciences and Mathematics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["© 2009, Elizabeth Ann Foley"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholarcommons.sc.edu/etd/28"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A new phenylene-linked multitopic family of bis(pyrazolyl)methane ligands, (C6H6-n[CH2OCH2CH(pz)2]2)n, where pz is a pyrazolyl ring, has been synthesized by the general reaction of (pz)2CHCH2OH with NaH, followed by the addition of C6H6-n[CH2Br]n. The silver(I) complexes of ligand o-C6H4[CH2OCH2CH(pz)2]2 form coordination polymer. The two other ditopic ligands, which have meta- and para-oriented \"arms\" (-CH2OCH2CH(pz)2), were treated with Ag(I) salts and recrystallized from acetone or acetonitrile to give nine silver(I) complexes, in which the four pyrazolyl rings of the ligand chelate a single silver(I) cation in a distorted tetrahedral environment forming unusually sized mononuclear metallacycles. The silver(I) complexes of the tetratopic and hexatopic ligands form double, mononuclear metallacycles, a new structural form. In the silver complexes of the tetratopic ligand, the double, mononuclear metallacycles are formed by two pairs of para-oriented arms chelating two silver ions on opposite sides of the central arene ring. The silver complexes of the hexatopic ligand also form double, mononuclear metallacycles; however, one metallacycle is formed by para-oriented arms and the other metallacycle is formed by meta-oriented arms. The remaining two arms link these metallacyles into coordination polymers.
The more rigid, ditopic, bis(pyrazolyl)methane ligand m-[CH(pz)2]2C6H4, Lm, yields the monofluoride bridged, binuclear [M2(μ-F)(μ-Lm)2](BF4)3 complexes when treated with M(BF4)2*xH2O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of Lm with Ni(BF4)2*6H2O yields dibridged [Ni2(μ-F)2(μ-Lm)2](BF4)2. The solid state structures
of seven [M2(μ-F)(μ-Lm)2](BF4)3 complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe2(μ-F)(μ-Lm)2](BF4)3 and [Co2(μ-F)(μ-Lm)2](BF4)3complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with J values of -10.4 and -0.67 cm-1, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu2(μ-F)(μ-Lm)2](BF4)3 are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm-1 or more negative.
Because of unusually large J value in [Cu2(μ-F)(μ-Lm)2](BF4)3, the complexes [Cu2(μ-Cl)(μ-Lm)2](BF4)3, [Cu2(μ-Cl)(μ-Lm)2](ClO4)3, [Cu2(μ-OH)(μ-Lm)2](ClO4)3, and [Cu2(μ-Br)(μ-Lm)2](BF4)3 were synthesized. The solid state structures of the [Cu2(μ-Cl)(μ-Lm)2]3+ complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu2(μ-OH)(μ-Lm)2]3+ complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.
nylene-linked multitopic family of bis(pyrazolyl)methane ligands, m-[CH(pz)2]2C6H4, Lm, yields the monofluoride bridged, binuclear [M2(μ-F)(μ-Lm)2](BF4)3 complexes when treated with M(BF4)2*xH2O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of Lm with Ni(BF4)2*6H2O yields dibridged [Ni2(μ-F)2(μ-Lm)2](BF4)2. The solid state structuresof seven [M2(μ-F)(μ-Lm)2](BF4)3 complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe2(μ-F)(μ-Lm)2](BF4)3 and [Co2(μ-F)(μ-Lm)2](BF4)3complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with J values of -10.4 and -0.67 cm-1, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu2(μ-F)(μ-Lm)2](BF4)3 are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm-1 or more negative.
Because of unusually large J value in [Cu2(μ-F)(μ-Lm)2](BF4)3, the complexes [Cu2(μ-Cl)(μ-Lm)2](BF4)3, [Cu2(μ-Cl)(μ-Lm)2](ClO4)3, [Cu2(μ-OH)(μ-Lm)2](ClO4)3, and [Cu2(μ-Br)(μ-Lm)2](BF4)3 were synthesized. The solid state structures of the [Cu2(μ-Cl)(μ-Lm)2]3+ complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu2(μ-OH)(μ-Lm)2]3+ complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.
"]},{"key":"dc:title","label":"Title","values":["Synthesis and Characterization of Transition Metal Complexes of Multitopic, Third-Generation, Phenylene-Linked Bis(1-Pyrazolyl)Methane Ligands"]}]}],"canonical_facts":{"dc:contributor":["Daniel L. Reger"],"dc:creator":["Foley, Elizabeth Ann"],"dc:description.abstract":["A new phenylene-linked multitopic family of bis(pyrazolyl)methane ligands, (C6H6-n[CH2OCH2CH(pz)2]2)n, where pz is a pyrazolyl ring, has been synthesized by the general reaction of (pz)2CHCH2OH with NaH, followed by the addition of C6H6-n[CH2Br]n. The silver(I) complexes of ligand o-C6H4[CH2OCH2CH(pz)2]2 form coordination polymer. The two other ditopic ligands, which have meta- and para-oriented \"arms\" (-CH2OCH2CH(pz)2), were treated with Ag(I) salts and recrystallized from acetone or acetonitrile to give nine silver(I) complexes, in which the four pyrazolyl rings of the ligand chelate a single silver(I) cation in a distorted tetrahedral environment forming unusually sized mononuclear metallacycles. The silver(I) complexes of the tetratopic and hexatopic ligands form double, mononuclear metallacycles, a new structural form. In the silver complexes of the tetratopic ligand, the double, mononuclear metallacycles are formed by two pairs of para-oriented arms chelating two silver ions on opposite sides of the central arene ring. The silver complexes of the hexatopic ligand also form double, mononuclear metallacycles; however, one metallacycle is formed by para-oriented arms and the other metallacycle is formed by meta-oriented arms. The remaining two arms link these metallacyles into coordination polymers.
The more rigid, ditopic, bis(pyrazolyl)methane ligand m-[CH(pz)2]2C6H4, Lm, yields the monofluoride bridged, binuclear [M2(μ-F)(μ-Lm)2](BF4)3 complexes when treated with M(BF4)2*xH2O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of Lm with Ni(BF4)2*6H2O yields dibridged [Ni2(μ-F)2(μ-Lm)2](BF4)2. The solid state structures
of seven [M2(μ-F)(μ-Lm)2](BF4)3 complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe2(μ-F)(μ-Lm)2](BF4)3 and [Co2(μ-F)(μ-Lm)2](BF4)3complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with J values of -10.4 and -0.67 cm-1, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu2(μ-F)(μ-Lm)2](BF4)3 are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm-1 or more negative.
Because of unusually large J value in [Cu2(μ-F)(μ-Lm)2](BF4)3, the complexes [Cu2(μ-Cl)(μ-Lm)2](BF4)3, [Cu2(μ-Cl)(μ-Lm)2](ClO4)3, [Cu2(μ-OH)(μ-Lm)2](ClO4)3, and [Cu2(μ-Br)(μ-Lm)2](BF4)3 were synthesized. The solid state structures of the [Cu2(μ-Cl)(μ-Lm)2]3+ complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu2(μ-OH)(μ-Lm)2]3+ complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.
nylene-linked multitopic family of bis(pyrazolyl)methane ligands, m-[CH(pz)2]2C6H4, Lm, yields the monofluoride bridged, binuclear [M2(μ-F)(μ-Lm)2](BF4)3 complexes when treated with M(BF4)2*xH2O, where M is Fe, Co, Cu, and Zn. In contrast, a similar reaction of Lm with Ni(BF4)2*6H2O yields dibridged [Ni2(μ-F)2(μ-Lm)2](BF4)2. The solid state structuresof seven [M2(μ-F)(μ-Lm)2](BF4)3 complexes show that the divalent metal ion is in a five-coordinate, trigonal bipyramidal, coordination environment with either a linear or nearly linear M-F-M bridging arrangement. In the solid state, the [Fe2(μ-F)(μ-Lm)2](BF4)3 and [Co2(μ-F)(μ-Lm)2](BF4)3complexes show weak intramolecular antiferromagnetic exchange coupling between the two metal(II) ions with J values of -10.4 and -0.67 cm-1, respectively; there is no observed long-range magnetic order. Three different solvates of [Cu2(μ-F)(μ-Lm)2](BF4)3 are diamagnetic between 5 and 400 K, thus showing strong antiferromagnetic exchange interactions of -600 cm-1 or more negative.
Because of unusually large J value in [Cu2(μ-F)(μ-Lm)2](BF4)3, the complexes [Cu2(μ-Cl)(μ-Lm)2](BF4)3, [Cu2(μ-Cl)(μ-Lm)2](ClO4)3, [Cu2(μ-OH)(μ-Lm)2](ClO4)3, and [Cu2(μ-Br)(μ-Lm)2](BF4)3 were synthesized. The solid state structures of the [Cu2(μ-Cl)(μ-Lm)2]3+ complexes show that the divalent copper ion is in a five-coordinate, trigonal bipyramidal, coordination environment with most of the monochloro bridges in a linear arrangement. The [Cu2(μ-OH)(μ-Lm)2]3+ complexes have a bent hydroxo bridge and a distorted square pyramidal coordination environment. In the solid state, all of these complexes are diamagnetic up to 350 K, which is indicative of very strong antiferromagnetic exchange interactions.
"],"dc:identifier":["https://scholarcommons.sc.edu/etd/28"],"dc:rights":["© 2009, Elizabeth Ann Foley"],"dc:subject":["Chemistry","Physical Sciences and Mathematics"],"dc:title":["Synthesis and Characterization of Transition Metal Complexes of Multitopic, Third-Generation, Phenylene-Linked Bis(1-Pyrazolyl)Methane Ligands"],"thesis:degree_discipline":["Chemistry and Biochemistry"],"thesis:degree_level":["Campus Access Dissertation"],"thesis:degree_name":["PhD"]},"updated_at":"2026-07-24T04:36:43Z"}