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Metal complexes of radical ligands

PGR-P-128

Key facts

Type of research degree
PhD
Application deadline
Ongoing deadline
Country eligibility
International (open to all nationalities, including the UK)
Funding
Competition funded
Supervisors
Professor Malcolm Halcrow
Schools
School of Chemistry
<h2 class="heading hide-accessible">Summary</h2>

Metal Complexes of Radical Ligands – Electron Hopping Leading to Novel Optical Properties This project involves the synthesis, electrochemistry and host:guest chemistry of metal complexes of redox-active (“non-innocent”) ligands. We are investigating metal complexes containing multiple redox-active organic ligand centres, with a view to producing a new class of mixed-valent molecules and materials. An example is cyclotricatechylene, a cyclic molecule containing three covalently linked catecholate groups that can each bind a metal ion. The platinum complex in the Figure exhibits three reversible low-potential oxidations in its cyclic voltammogram, corresponding to step-wise oxidation of its three catecholate groups to semiquinone radical centres: The radical oxidation products have intense colours, with strong absorptions in the visible and near-IR regions. This reflects the hopping of unpaired electrons around the macrocycle, between aromatic rings.Near-IR absorbers like these, whose absorptions can be switched on and off electronically, can be very useful in fibre-optic communications devices. Current work aims to add more steric protection to these ligand radicals, to improve their stability at room temperature; to incorporate these radicals into extended framework (“MOF”) structures with similar electron-hopping properties; and, to design new ligands with different numbers and topologies of redox centres. This project involves organic and inorganic synthesis, crystallography, electrochemistry and other techniques for studying radical products (EPR, UV/vis/NIR and IR spectroscopies, magnetic measurements and DF calculations).

<h2 class="heading">How to apply</h2>

<p>Formal applications for research degree study should be made online through the&nbsp;<a href="https://www.leeds.ac.uk/info/130206/applying/91/applying_for_research_degrees">University&rsquo;s website</a>. Please state clearly in the research information section&nbsp;that the research degree you wish to be considered for is &lsquo;Metal complexes of radical ligands&rsquo; as well as&nbsp;<a href="https://physicalsciences.leeds.ac.uk/staff/173/professor-malcolm-halcrow">Professor Malcolm Halcrow</a>&nbsp;as your proposed supervisor.</p> <p>If English is not your first language, you must provide evidence that you meet the University&#39;s minimum English language requirements (below).</p> <p><em>We welcome applications from all suitably-qualified candidates, but UK black and minority ethnic (BME) researchers are currently under-represented in our Postgraduate Research community, and we would therefore particularly encourage applications from UK BME candidates. All scholarships will be awarded on the basis of merit.</em></p>

<h2 class="heading heading--sm">Entry requirements</h2>

Applicants to research degree programmes should normally have at least a first class or an upper second class British Bachelors Honours degree (or equivalent) in an appropriate discipline. The criteria for entry for some research degrees may be higher, for example, several faculties, also require a Masters degree. Applicants are advised to check with the relevant School prior to making an application. Applicants who are uncertain about the requirements for a particular research degree are advised to contact the School or Graduate School prior to making an application.

<h2 class="heading heading--sm">English language requirements</h2>

The minimum English language entry requirement for research postgraduate research study is an IELTS of 6.0 overall with at least 5.5 in each component (reading, writing, listening and speaking) or equivalent. The test must be dated within two years of the start date of the course in order to be valid. Some schools and faculties have a higher requirement.

<h2 class="heading">Funding on offer</h2>

<p><strong>Self-Funding Students</strong></p> <p><strong>Funding Eligibility</strong></p> <p><strong>UK/EU</strong> &ndash;&nbsp;Leeds Doctoral Scholarship Award paying Academic Fees and Maintenance matching EPSRC rate of &pound;15,009 per year for 3 years, Lowson Research Scholarship &amp; John Henry Garner paying Academic Fees and Maintenance at a fixed rate of &pound;14,000 per year for 3 years, School of Chemistry Scholarship award paying Academic Fees and Maintenance matching EPSRC rate of &pound;15,009 per year for 3 years.&nbsp; Alumni Bursary is available to previous University of Leeds graduates offering 10% discount on Academic Fees.</p> <p><strong>International Students</strong> &ndash;&nbsp;China Scholarship Council-University of Leeds Scholarship Award paying Academic Fees for 3 years,&nbsp;School of Chemistry Scholarship award paying Academic Fees for 3 years, Commonwealth Scholarship and Commonwealth Split Site Scholarships.&nbsp; Alumni Bursary is available to previous University of Leeds graduates offering 10% discount on Academic Fees.</p>

<h2 class="heading">Contact details</h2>

<p>For further information please contact Doctoral College Admissions by&nbsp;email: <a href="mailto:maps.pgr.admissions@leeds.ac.uk">maps.pgr.admissions</a><a href="mailto:EMAIL@leeds.ac.uk">@leeds.ac.uk</a>, or by telephone: +44 (0)113 343 5057.</p>


<h3 class="heading heading--sm">Linked funding opportunities</h3>