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Click chemistry inside porous metal-organic framework

   Faculty of Life Sciences

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  Dr Anna Wu, Dr Sanjit Nayak  No more applications being accepted  Self-Funded PhD Students Only

About the Project

Suitably qualified and highly motivated candidates are invited to apply for a self-funded 3.5-year PhD studentship in the group of Dr. Anna Wu (co-supervised by Dr. Sanjit Nayak) at University of Bradford in the area of organic chemistry synthesis and inorganic synthesis. Metal-organic frameworks (MOFs) are a class of compounds consisting of metal clusters coordinated to organic ligands to form three-dimensional structures containing potential voids. The pores can be filled with guest molecules and are interest for click chemistry. 

Click reactions occur in one pot, generate minimal by-products, and afford irreversibly high yields of a single reaction product, with high reaction specificity. In this project we propose to synthesize and post-synthetically modify an electron-rich alkyne-tagged zirconium-based metal-organic framework and use the pore of MOF as a nano-vessel to impose on the click reaction. The benefits of nano-vessel methods are for protection of these substances in the adverse environment. The alkynyl groups in the pore surface will be subjected to a “click” chemistry—[2+2] cycloaddition and cascade retro-electrocyclisation (CA-RE). This methodology is atom-economic, using ‘click’ concept and doesn’t require a catalyst (metal-free). The ‘click’-chemistry allows us to anchor other desired functional groups (cyano, amino) onto the pore walls, enabling more potential applications, such as the storage of gases, fluorescence switch (via amine addition to cyano groups to turn off the fluorescence quenching effect) and electron storage (cyano group accepts electrons, amino group donates electrons). This development of this click methodology is of great significance and will focus on catalyst-free, environmentally green merits, therefore, it must be a benefit to the chemical industry. 


The student will receive in-depth training in a wide range of synthetic organic, inorganic chemistry synthesis, and a diverse array of analytical techniques including NMR spectroscopy, mass spectrometry, IR spectroscopy, thermal analyses, scanning electron microscopy, and X-ray diffraction.

The ideal candidate will hold (or expect to be awarded) a 1st Class or an Upper 2nd Class MSc, MChem or BSc degree and will have significant experience in practical synthetic organic chemistry. The student will be required to undertake complex multistep organic synthesis involving air- and / or moisture-sensitive reagents and unstable synthetic intermediates, and will be expected to possess excellent laboratory skills, good problem-solving abilities and the ability to obtain and interpret spectroscopic data. Anticipated Start Date: 1st June 2022.

Funding Notes

This is a self-funded PhD project; applicants will be expected to pay their own fees or have a suitable source of third-party funding. A bench fee may also apply to this project, in addition to the tuition fees. UK students may be able to apply for a Doctoral Loan from Student Finance for financial support.


[1] Synthesis of Sulfonamide-Based Ynamides and Ynamines in Water, Lei Zhao, Hongyi Yang, Ruikun Li, Ye Tao, Xiao-Feng Guo, Edward A. Anderson, Andy Whiting and Na Wu*, J. Org. Chem., 2020, 86(2), 1938.
[2] The Chemistry of Ynamide and Its Application in Organic Synthesis, Siyu Ye and Na Wu*, eds: A. Rahma, Advances in Organic Synthesis, the Netherlands, 2020, volume 13, chapter 2, ISBN: 978-981-14-0509-9.
[3] Mixed-linker approach in designing porous zirconium-based metal–organic frameworks with high hydrogen storage capacity, A. Naeem, V. P. Ting, U. Hintermair, M. Tian, R. Telford, Saaiba Halim, H. Nowell, M. Hołyńska, S. J. Teat, I. J. Scoweng and S. Nayak*, Chem. Commun., 2016, 52, 7826.
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