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Synthesis of supramolecular iron (II...

Seddon, Elisa Joy.

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Synthesis of supramolecular iron (III) complexes by cluster aggregation.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Synthesis of supramolecular iron (III) complexes by cluster aggregation./
Author:	Seddon, Elisa Joy.
Description:	230 p.
Notes:	Source: Dissertation Abstracts International, Volume: 62-02, Section: B, page: 0857.
Contained By:	Dissertation Abstracts International62-02B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3005409
ISBN:	049314692X

Synthesis of supramolecular iron (III) complexes by cluster aggregation.
Seddon, Elisa Joy.

Synthesis of supramolecular iron (III) complexes by cluster aggregation. - 230 p.

Source: Dissertation Abstracts International, Volume: 62-02, Section: B, page: 0857.

Thesis (Ph.D.)--Indiana University, 2000.

Biologically, iron is a ubiquitous and versatile metal, found in the active sites of proteins responsible for both oxygen and electron transport. Multinuclear iron-oxo proteins are either dinuclear, or contain many iron atoms; the [Fe2O] unit occurs in hemerythrin (Hr), ribonucleotide reductase, purple acid phosphatase (POP) and methane monooxygenase (MMO), whereas ferritin (Ft) can store up to 4500 iron atoms. Iron storage and transport are essential for protecting biological organisms from free iron, since free Fe(II) ions, will react with dioxygen to form destructive organic radicals, and free Fe(III) ions form insoluble iron hydroxide aggregates under physiological conditions.

ISBN: 049314692XSubjects--Topical Terms:

517253
Chemistry, Inorganic.

Synthesis of supramolecular iron (III) complexes by cluster aggregation.
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100 1 $a Seddon, Elisa Joy. $3 1932969
245 1 0 $a Synthesis of supramolecular iron (III) complexes by cluster aggregation.
300 $a 230 p.
500 $a Source: Dissertation Abstracts International, Volume: 62-02, Section: B, page: 0857.
500 $a Chairman: George Christou.
502 $a Thesis (Ph.D.)--Indiana University, 2000.
520 $a Biologically, iron is a ubiquitous and versatile metal, found in the active sites of proteins responsible for both oxygen and electron transport. Multinuclear iron-oxo proteins are either dinuclear, or contain many iron atoms; the [Fe2O] unit occurs in hemerythrin (Hr), ribonucleotide reductase, purple acid phosphatase (POP) and methane monooxygenase (MMO), whereas ferritin (Ft) can store up to 4500 iron atoms. Iron storage and transport are essential for protecting biological organisms from free iron, since free Fe(II) ions, will react with dioxygen to form destructive organic radicals, and free Fe(III) ions form insoluble iron hydroxide aggregates under physiological conditions.
520 $a The tendency of iron to form molecular aggregates in systems containing water or alcohol, together with the fact that each iron atom possesses a large number of unpaired electrons (5 for high-spin FeIII) often results in products possessing large spin ground states (S). The current record-holder for iron is a Fe19 complex, with at least 33 unpaired electrons in the ground state (S = 33/2). Hence, iron is also important in the rapidly developing field of molecular magnetic materials. For these two reasons, the preparation of iron clusters with new topologies and properties has become a major goal of many synthetic inorganic groups, including our own.
520 $a In this thesis work, synthetic and spectroscopic methods of inorganic coordination chemistry were used to achieve two different goals: firstly, to synthesize dinuclear iron complexes with the use of tetradentate ligands in order to study the magnetic interactions between the two metal centers; and secondly, to identify reactions and characterize the products whereby pre-formed iron oxide clusters undergo aggregation reactions to produce higher nuclearity products. The tetradentate ligands investigated were a bis-(beta-diketone) ligand L and a bis-bpy ligand L'. The reactions involving L and Fe(III) reagents produced complexes with a triple-helical structure; both the meso and helical forms of Fe2(L)3 were crystallographically characterized. In this work, suitable reaction conditions were found whereby dinuclear complexes of the form [Fe2OX2(O2CR) 2L'] (X = Cl or Br; R = CH3 or C 6H5) could be formed via self-assembly. The choice of solvent proved to be an important variable; the complex [Fe 6O6(O2CPh)3L' 3(H2O)2]3+ with a "six-rung ladder" core was produced from the same reactant stoichiometry as the dinuclear complexes, but in a different solvent. Controlled alcoholysis of pre-formed Fe4 or Fe3 complexes was used as a new method to induce cluster aggregation, and mixed oxide-alkoxide-carboxylate complexes of Fe6 or Fe7, as well as the cyclic complex [Fe(OCH 3)2(O2CCH3)]10 were synthesized via this method. The products were spectroscopically, electrochemically, and magnetochemically characterized.
590 $a School code: 0093.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Engineering, Materials Science. $3 1017759
690 $a 0488
690 $a 0794
710 2 0 $a Indiana University. $3 960096
773 0 $t Dissertation Abstracts International $g 62-02B.
790 1 0 $a Christou, George, $e advisor
790 $a 0093
791 $a Ph.D.
792 $a 2000
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3005409