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Synthesis and properties of manganes...
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Canada Vilalta, Cristina.
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Synthesis and properties of manganese and iron carboxylate clusters.
Record Type:
Electronic resources : Monograph/item
Title/Author:
Synthesis and properties of manganese and iron carboxylate clusters./
Author:
Canada Vilalta, Cristina.
Description:
298 p.
Notes:
Source: Dissertation Abstracts International, Volume: 64-06, Section: B, page: 2662.
Contained By:
Dissertation Abstracts International64-06B.
Subject:
Chemistry, Inorganic. -
Online resource:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3094091
ISBN:
0496417932
Synthesis and properties of manganese and iron carboxylate clusters.
Canada Vilalta, Cristina.
Synthesis and properties of manganese and iron carboxylate clusters.
- 298 p.
Source: Dissertation Abstracts International, Volume: 64-06, Section: B, page: 2662.
Thesis (Ph.D.)--Indiana University, 2003.
Manganese and iron are found in the active center of a number of metallobiomolecules. Besides their biological relevance, these metals form polynuclear species that often display large ground-state spins values of significance in molecular magnetism. For both reasons, there is much interest in the development of synthetic procedures to prepare new complexes of manganese and iron.
ISBN: 0496417932Subjects--Topical Terms:
517253
Chemistry, Inorganic.
Synthesis and properties of manganese and iron carboxylate clusters.
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Synthesis and properties of manganese and iron carboxylate clusters.
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298 p.
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Source: Dissertation Abstracts International, Volume: 64-06, Section: B, page: 2662.
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Chair: George Christou.
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Thesis (Ph.D.)--Indiana University, 2003.
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Manganese and iron are found in the active center of a number of metallobiomolecules. Besides their biological relevance, these metals form polynuclear species that often display large ground-state spins values of significance in molecular magnetism. For both reasons, there is much interest in the development of synthetic procedures to prepare new complexes of manganese and iron.
520
$a
In this thesis work, diverse synthetic routes were developed that allowed access to a number of compounds with new topologies and properties. Selective carboxylate and chelate exchange, oxidation, and comproportionation reactions were some of the synthetic routes used to prepare different manganese compounds. The tetranuclear compound [Mn4O2(O2CPh) 6(dpm)2] (dpm- = anion of dipivaloylmethane), has proved to be an excellent starting material for selective chelate replacement by more acidic chelating ligands, leaving the Mn/O/carboxylate core intact. The use of the dicarboxylic acid mpdpH2 (m-phenylenedipropionic acid) has allowed the preparation of [Mn6O7(mpdp) 3(bpy)3](ClO4), which has an unprecedented hexanuclear structure containing a [Mn4O4]5+ subunit that can be identified as an isomer of one of the topologies proposed for the WOC based on EXAFS results.
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The aggregation of polynuclear complexes triggered by reaction with alcohols, chelating ligands, or pyridine was explored as a means to prepare iron clusters. This has afforded a number of compounds with different nuclearities and topologies, such as the hexanuclear complexes [Fe6O2(OH)2(O 2CR)10(hep)2] and [Fe6O2(OH)(O 2CR)9(hep)4], which are structurally analogous but display ground states with very different spin. Other notable compounds include the eight-membered rings [Fe8(OH)4(OPh) 8(O2CR)12] and the iron-centered [Fe7O 3(H2O)(OMe)6(O2CMe)6(py) 6](ClO4)3, among others.
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The physical properties of these compounds were investigated by spectroscopic, electrochemical and magnetochemical techniques. Particular attention was devoted to the of the magnetic properties, exchange interactions and ground state spins, and the investigation of the relationship between those and structural parameters. Understanding these factors is particularly valuable for the rational synthetic design of molecules with desired magnetic properties.
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School code: 0093.
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Chemistry, Inorganic.
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Indiana University.
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http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3094091
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