St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • Chemistry (School of)
  • Chemistry
  • Chemistry Theses
  • View Item
  •   St Andrews Research Repository
  • Chemistry (School of)
  • Chemistry
  • Chemistry Theses
  • View Item
  •   St Andrews Research Repository
  • Chemistry (School of)
  • Chemistry
  • Chemistry Theses
  • View Item
  • Register / Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Synthesis, structure and properties of carboxylate coordination polymers

Thumbnail
View/Open
RebeccaClulowPhDThesis.pdf (44.92Mb)
Date
03/12/2019
Author
Clulow, Rebecca
Supervisor
Lightfoot, Philip
Funder
Engineering and Physical Sciences Research Council (EPSRC)
University of St Andrews. School of Chemistry
Grant ID
EP/K503162-1
Metadata
Show full item record
Abstract
The work in this thesis focuses on several coordination polymers, their crystal structures and their potential applications as functional materials, in particular, their ferroelectric and magnetic properties. The mechanism of the known ferroelectric phase transition of (C₃NO₂H₇)₃CaCl₂ (TSCC) was studied in detail using both X-ray and neutron diffraction data. The key structural changes occurring in the vicinity of TC were identified in the Ca-O-C bond angles, which change by up to 12˚. The structure of the compound was determined between 300 and 20 K to investigate potential phase transitions as suggested in the literature. The diffraction data did not suggest an additional phase transition within this temperature range. However, the detailed crystallographic studies did uncover new evidence of ferrielectricity, which is consistent with electrical hysteresis data. The origins of the ferroelectricity of TSCC were also probed through the synthesis and characterisation of a range TSCC-related compounds which incorporated a range of alternative halides and metal 2+ cations. Each compound formed coordination polymers which were linked by sarcosine molecules, although the connectivity and structures formed were dependent upon the composition. Whilst none of the TSCC derivatives had ferroelectric properties, diffraction experiments were limited to a low temperature of 90 K and there could be additional phase transitions below this point. A family of oxalate-based coordination polymers ALi₃M(C₂O₄)₃ with a perovskite-like structures were also synthesised. The structural flexibility of these systems was investigated through the incorporation of different A site cations and their magnetic properties were investigated. Polyhedral distortions increase significantly upon the inclusion of rubidium or caesium. Both KLi₃Co(C₂O₄)₃ and KLi₃Ni(C₂O₄)₃ have weak antiferromagnetic exchange and μ[sub](eff) of 4.82 μ[sub]B and 3.62 μ[sub]B, respectively. The syntheses and structures of four new oxalate containing compounds, namely Rb₂Co(C₂O₄)₂.4H₂O, Rb₂CoCl₂(C₂O₄), K₂Li₂Cu(C₂O₄)₃ and Li₄Co(C₂O₄)₃, which could have interesting magnetic and electrochemical properties, are also reported.
DOI
https://doi.org/10.17630/10023-18591
Type
Thesis, PhD Doctor of Philosophy
Collections
  • Chemistry Theses
Description of related resources
Synthesis, structure and properties of carboxylate coordination polymers (Thesis data) Clulow, R., University of St Andrews. DOI: https://doi.org/10.17630/000ddea9-f1d9-4ef7-b7e4-b57342d69fe4
Related resources
https://doi.org/10.17630/000ddea9-f1d9-4ef7-b7e4-b57342d69fe4
URI
http://hdl.handle.net/10023/18591

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter