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Metal complexes of radical ligands


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Key facts

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

Metal Complexes of Radical Ligands &ndash; Electron Hopping Leading to Novel Optical Properties<br /> <br /> This project involves the synthesis, electrochemistry and host: guest chemistry of metal complexes of redox-active (non-innocent) ligands.<br /> <br /> 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:<br /> <br /> 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.<br /> <br /> 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="">University&rsquo;s website</a>. Please state clearly in the Planeed Course of Study section that you are applying for <em><strong>PHD Chemistry FT</strong></em> and&nbsp;in the research information section&nbsp;that the research degree you wish to be considered for is <em><strong>Metal complexes of radical ligands</strong></em>&nbsp;as well as&nbsp;<a href="">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>&nbsp;</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-Funded or externally sponsored students are welcome to apply.</strong></p> <p><strong>UK&nbsp;</strong>&ndash;&nbsp;The&nbsp;<a href="">Leeds Doctoral Scholarships</a>,&nbsp;<a href="">Lund Stephenson Clarke</a>, <a href="">Akroyd &amp; Brown</a>, <a href="">Frank Parkinson</a>, <a href="">Henry Ellison-Charles Brotherton</a> and <a href="">Boothman, Reynolds &amp; Smithells</a> Scholarships are available to UK applicants. &nbsp;<a href="">Alumni Bursary</a> is available to graduates of the University of Leeds.</p> <p><strong>Non-UK</strong>&nbsp;&ndash;The&nbsp;<a href="">China Scholarship Council - University of Leeds Scholarship</a>&nbsp;is available to nationals of China. The&nbsp;<a href="">Leeds Marshall Scholarship</a>&nbsp;is available to support US citizens. &nbsp;<a href="">Alumni Bursary</a> is available to graduates of the University of Leeds.</p> <p>Please refer to the <a href="">UKCISA</a> website for information regarding Fee Status for Non-UK Nationals starting from September/October 2021.</p>

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

<p>For further information regarding your application, please contact Doctoral College Admissions by&nbsp;email: <a href="">maps.pgr.admissions</a><a href=""></a>, or by telephone: +44 (0)113 343 5057.</p> <p>For further information about this project, please contact Professor Malcolm Halcrow by&nbsp;email:&nbsp;<a href=""></a></p>