Funding
Funded
Axially Chiral Salts for Sensing and Catalysis
School of Chemistry and Chemical Engineering | PHD
Applications are now CLOSED
Reference Number
SCCE-2022-008
Application Deadline
25 February 2022
Start Date
3 October 2022
Overview
Axial chirality is typically exemplified by homobiaryl compounds such as BINAP and BINOL. These structures are ubiquitous in asymmetric catalysis, where they function as ligands or organocatalysts. The analogous hetero-biaryl compounds containing a N-C axis are formally cationic at nitrogen due to its trivalency. These are interesting since they bear the axial chirality of neutral homobiaryls, as well as the ability to form ion pairs and participate in supramolecular charge-charge interactions. We recently reported the first enantioselective synthetic methodology approach towards this class of compound. The N-arylquinolinium salts displayed high barriers to racemisation (>~40 kcal/mol) and solvatochromism in their UV-vis and fluorescence spectra.
We will synthesise a novel library of diverse cationic N+-C heterobiaryl atropisomers and explore their sensory and catalytic applications. Neutral axially chiral frameworks will be synthesised as previously reported in the literature, followed by quaternization to afford the corresponding novel salts. Benzimidazoles will be alkylated on N(3) to afford the corresponding benzimidazolium cations, while those substrates bearing a pyridone functionality will either be directly alkylated on oxygen or activated prior to cross-coupling at this position (e.g. Tf2O then Suzuki/Stille). We have already performed a proof-of-concept reaction using Meerwein’s salt, and the quaternization proceeds with complete retention of axial chirality. Temperature is crucial in these asymmetric syntheses, so where appropriate we will use our expertise in continuous flow chemistry to achieve thermal control. We will also explore novel approaches to N-C axes using Rh(II)-catalysed carbene insertion. An interesting extension would be to form axially chiral C+-C axes, which are known, stable intermediates in the synthesis of numerous triangulenes. We have shown that N-arylquinolinium salts display solvatochromism in their fluorescence spectra. We will explore this effect across the library of cationic compound classes using fluorescence and UV-vis plate readers to enable rapid data acquisition, allowing structure-activity relationships to be established. Chiroptical Properties. Of particular interest is chirosolvatochromism, where the cationic molecules display different absorption or emission behaviour in the presence of one or other enantiomer of a chiral solvent, or in the presence of chiral additives. This could provide a method for high-throughput optical measurement of ee, which can be a bottleneck in the development of catalytic asymmetric reactions. Solid (ssNMR, XRD) and solution-phase (NMR) techniques will be used to understand the structure of the complexes formed.
Candidates must possess or expect to obtain, a 2:1 or first-class degree in Chemistry or closely related discipline.
Funding Information
The studentships detailed are open to UK and ROI nationals, or EU nationals that have obtained settled status in the UK. Full eligibility information can be viewed via: https://www.nidirect.gov.uk/articles/department-economy-postgraduate-studentship-scheme
Project Summary
Supervisor
Dr Peter Knipe
Mode of Study
Full-time: 3 years
Funding Body
Department for Economy
Chemistry overview
The School of Chemistry and Chemical Engineering aims to promote sustainable processes and materials to meet the energy and healthcare demands of the future. The School is expanding rapidly and this is creating many new and exciting research opportunities with over £15m being invested to develop and expand the core research areas of catalysis, biological and medicinal chemistry, and materials.
Mode of study / duration
Registration is on a full-time or part-time basis, under the direction of a supervisory team appointed by the University. You will be expected to submit your thesis at the end of three years of full-time registration for PhD, or two years for MPhil (or part-time equivalent).
Key Facts
QUB is a member of the Russell Group of the UK’s 24 leading research-intensive universities.
- QUB is ranked =13th in the UK for research intensity
QUB is ranked 9th in the UK for Graduate Prospects – Outcomes (Complete University Guide 2025) - Over 99% of Queen’s research environment was assessed as world-leading or internationally excellent in REF2021
88% of research submitted by Queen’s has been assessed as world-leading or internationally excellent in REF2021 - 83% of Research Impact case studies by the School has been assessed as world-leading or internationally excellent REF2021, placing it among the top UK universities for Research Impact
Course content
Research Information
Associated Research
Much of our research falls under the broad headings of Healthcare and Sustainability, examples of recent funded projects include development of novel antibiotics and reduction of single use plastics. The School also leads the EU-funded Bryden Centre for renewable energy research, the industry-led Centre for Advanced Sustainable Energy (CASE) as well as our world-leading QUILL ionic liquids research centre. Students trained in our School are equipped with the skills that allow them to go out and make a real difference in the world.
Our areas of interest include adventurous research at the cutting edge of catalysis (where chemistry meets other disciplines, especially engineering, innovative Molecular Materials and Functional Materials), ionic liquid technology (‘super solvents' which do not form vapours and can be used as non-polluting alternatives to conventional solvents) and Synthesis and Biological Organic Chemistry (working to deliver compounds addressing the regulation of cellular functions).
QUILL (Queen's University Ionic Liquid Laboratories): the largest multidisciplinary research group in the world centred on ionic liquid technology, whose work on ‘super solvents' (which do not form vapours and can be used as non-polluting alternatives to conventional solvents) was voted ‘Most Important British Innovation of the 21st Century' in 2013.
All of our research groups have significant links with researchers and other institutions globally, and there are opportunities for collaboration and study visits, etc.
We have extensive links with industry, meaning that employment prospects for our graduates are excellent.
Much of our research is interdisciplinary, and our students can broaden their experience and knowledge by working with researchers from other disciplines (eg biologists, physicists).
Career Prospects
Introduction
For further information on career opportunities at PhD level please contact the Faculty of Engineering and Physical Sciences Student Recruitment Team on askEPS@qub.ac.uk.
Our advisors - in consultation with the School - will be happy to provide further information on your research area, possible career prospects and your research application.
People teaching you
Professor John Holbrey
Director of Postgraduates
Chemistry&Chemical Engineering
Email: J.Holbrey@qub.ac.uk
Course structure
-Entrance requirements
Graduate
The minimum academic requirement for admission to a research degree programme is normally an Upper Second Class Honours degree from a UK or ROI HE provider, or an equivalent qualification acceptable to the University. Further information can be obtained by contacting the School.
International Students
For information on international qualification equivalents, please check the specific information for your country.
English Language Requirements
Evidence of an IELTS* score of 6.0, with not less than 5.5 in any component, or an equivalent qualification acceptable to the University is required (*taken within the last 2 years).
International students wishing to apply to Queen's University Belfast (and for whom English is not their first language), must be able to demonstrate their proficiency in English in order to benefit fully from their course of study or research. Non-EEA nationals must also satisfy UK Visas and Immigration (UKVI) immigration requirements for English language for visa purposes.
For more information on English Language requirements for EEA and non-EEA nationals see: www.qub.ac.uk/EnglishLanguageReqs.
If you need to improve your English language skills before you enter this degree programme, INTO Queen's University Belfast offers a range of English language courses. These intensive and flexible courses are designed to improve your English ability for admission to this degree.
Tuition Fees
| Northern Ireland (NI) 1 | TBC |
| Republic of Ireland (ROI) 2 | TBC |
| England, Scotland or Wales (GB) 1 | TBC |
| EU Other 3 | £25,600 |
| International | £25,600 |
1 EU citizens in the EU Settlement Scheme, with settled or pre-settled status, are expected to be charged the NI or GB tuition fee based on where they are ordinarily resident, however this is provisional and subject to the publication of the Northern Ireland Assembly Student Fees Regulations. Students who are ROI nationals resident in GB are expected to be charged the GB fee, however this is provisional and subject to the publication of the Northern Ireland Assembly student fees Regulations.
2 It is expected that EU students who are ROI nationals resident in ROI will be eligible for NI tuition fees. The tuition fee set out above is provisional and subject to the publication of the Northern Ireland Assembly student fees Regulations.
3 EU Other students (excludes Republic of Ireland nationals living in GB, NI or ROI) are charged tuition fees in line with international fees.
All tuition fees quoted are for the academic year 2021-22, and relate to a single year of study unless stated otherwise. Tuition fees will be subject to an annual inflationary increase, unless explicitly stated otherwise.
More information on postgraduate tuition fees.
Chemistry costs
Additional course costs
All Students
Depending on the programme of study, there may also be other extra costs which are not covered by tuition fees, which students will need to consider when planning their studies . Students can borrow books and access online learning resources from any Queen's library. If students wish to purchase recommended texts, rather than borrow them from the University Library, prices per text can range from £30 to £100. Students should also budget between £30 to £100 per year for photocopying, memory sticks and printing charges. Students may wish to consider purchasing an electronic device; costs will vary depending on the specification of the model chosen. There are also additional charges for graduation ceremonies, and library fines. In undertaking a research project students may incur costs associated with transport and/or materials, and there will also be additional costs for printing and binding the thesis. There may also be individually tailored research project expenses and students should consult directly with the School for further information.
Bench fees
Some research programmes incur an additional annual charge on top of the tuition fees, often referred to as a bench fee. Bench fees are charged when a programme (or a specific project) incurs extra costs such as those involved with specialist laboratory or field work. If you are required to pay bench fees they will be detailed on your offer letter. If you have any questions about Bench Fees these should be raised with your School at the application stage. Please note that, if you are being funded you will need to ensure your sponsor is aware of and has agreed to fund these additional costs before accepting your place.
How do I fund my study?
1.PhD OpportunitiesFind PhD opportunities and funded studentships by subject area.
2.Funded Doctoral Training ProgrammesWe offer numerous opportunities for funded doctoral study in a world-class research environment. Our centres and partnerships, aim to seek out and nurture outstanding postgraduate research students, and provide targeted training and skills development.
3.PhD loansThe Government offers doctoral loans of up to £26,445 for PhDs and equivalent postgraduate research programmes for English- or Welsh-resident UK and EU students.
4.International ScholarshipsInformation on Postgraduate Research scholarships for international students.
Funding and Scholarships
The Funding & Scholarship Finder helps prospective and current students find funding to help cover costs towards a whole range of study related expenses.
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Apply using our online Postgraduate Applications Portal and follow the step-by-step instructions on how to apply.
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