Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes

Bibliographic Details
Main Author:	Gaffen, Joshua R.
Language:	English
Published:	Case Western Reserve University School of Graduate Studies / OhioLINK 2018
Subjects:	Inorganic Chemistry
Online Access:	http://rave.ohiolink.edu/etdc/view?acc_num=case1513801198165435

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spelling	ndltd-OhioLink-oai-etd.ohiolink.edu-case15138011981654352021-08-03T07:05:08Z Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes Gaffen, Joshua R. Inorganic Chemistry The incorporation of heteroatoms into carbon-based systems for the modification of functional materials is an exciting field of study. Of relatively recent interest is the addition of phosphorus to traditionally all-carbon systems, which is possible due to the similarities between the two elements, affording unique chemical and electronic properties. Herein, permutations of o-hydroxyarl phosphines and phosphine oxides were developed for two distinct functions. The compounds start from similar, readily available materials, and utilize similar syntheses.Bis(phosphonate) compounds were generated from aryl diols such as catechol and 2,3-dihydroxynaphthalene. These bis(phosphonate)s acted as chelates to main group elements like boron and phosphorus, and lithium salts were generated. These salts, designed to parallel lithium-ion battery electrolyte salts, had flame retardant properties. Therefore, these materials could potentially act as bifunctional electrolytes: flame retardant ions for lithium-ion batteries (FRIONs). This second generation of FRIONs was generated in good yields from commercially-available materials, and exhibited good flame retardant properties. Using a bottom-up design, modifications were made to these ligands to impart properties, such as solubility, to the resultant main group chelates and lithium salts. Several such modifications were made corresponding to the third generation of FRIONs.A new synthetic route utilizing a Lewis acid was developed for the synthesis of 1,3-benzoxaphosphole (BOP) compounds (Chapter 4), and a new reduction was developed for the generation of o-hydroxyarylphosphines, common BOP starting materials (Chapter 3). These methods allowed for isolation of previously synthesized BOP compounds (and starting materials) in nearly quantitative yields, and the generation of BOP compounds developed from FRION precursors. Using the new synthetic method of BOP synthesis, stepwise polymerization reactions were performed which resulted in the generation of several BOP-based oligomers. The choice of phosphine starting material and linker significantly impacted the results of the polymerization reaction. Using a terephthalate linker resulted in low degrees of polymerization due to p-stacking interactions, while fluorene linkers resulted in decomposition of the BOP unit due to slow reactivity. These new synthetic procedures were also used to generate novel BOP materials with unique reactivity (Chapters 7,8), and were utilized in attempts to generate other group 15 heterocycles (Chapter 6). 2018-02-01 English text Case Western Reserve University School of Graduate Studies / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=case1513801198165435 http://rave.ohiolink.edu/etdc/view?acc_num=case1513801198165435 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection	NDLTD
language	English
sources	NDLTD
topic	Inorganic Chemistry
spellingShingle	Inorganic Chemistry Gaffen, Joshua R. Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes
author	Gaffen, Joshua R.
author_facet	Gaffen, Joshua R.
author_sort	Gaffen, Joshua R.
title	Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes
title_short	Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes
title_full	Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes
title_fullStr	Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes
title_full_unstemmed	Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes
title_sort	functional main group materials: from flame retardant ions (frions) for lithium-ion batteries to polymeric oxaphospholes
publisher	Case Western Reserve University School of Graduate Studies / OhioLINK
publishDate	2018
url	http://rave.ohiolink.edu/etdc/view?acc_num=case1513801198165435
work_keys_str_mv	AT gaffenjoshuar functionalmaingroupmaterialsfromflameretardantionsfrionsforlithiumionbatteriestopolymericoxaphospholes
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Functional Main Group Materials: From Flame Retardant Ions (FRIONs) for Lithium-Ion Batteries to Polymeric Oxaphospholes

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