Projects per year
Highest citation count for a single research paper +625.
Current harassment level approx. 87%
For those who prefer Words
I was born and raised in Alexandria (the one in west-central Scotland, not the original Egyptian one, so imagine lots of rain and a distinct lack of pyramids) and was set on the path of chemistry by the wonderful teaching of Bob Horn at the Vale of Leven Academy.
Both my first degree and my PhD were from the University of Glasgow, the latter was in the synthesis and structure of organometallic (Rh, Ni, Pd) complexes and was supervised by Drs Ron Cross, Ken Muir and Lj. Manojlovic-Muir.
It soon became apparent that the ability to stick P to Rh (often in yields as high as 15%) was not a skill sought by prospective employers and so as the years passed I have moved more towards structural and crystallographic chemistry – a transformation completed to such an extent that I am now a co-editor of Acta Cryst. Section C.
After being a student, I held various post-doctoral type posts at both the University of Glasgow and across town at the University of Strathclyde. I also spent too much time at synchrotron sources. During this early period I set up Strathclyde's first single crystal X-ray diffraction laboratory and later I developed it into the modern multi-instrument facility that we now have.
Eventually Strathclyde decided to keep me, and since 2004 I've been a full member of lecturing staff in the inorganic chemistry (now called synthesis and catalysis) section. This is somewhat odd as I know very little about synthesis and close to zero about catalysis.
I work in a variety of areas, but it can all broadly be described as attempting to discover what materials’ structures can tell us about their chemical or physical properties.
As described in more detail below, my interests developed largely from early contacts with the work of Rab Mulvey (s-block metals), Ewen Smith (dyes and pigments) and the Solid-State group in what was Strathclyde's Pharmacy Dept. aka Alastair Florence and Norman Shankland (pharmaceutical materials).
So far this has led to around 600 publications - lately at a rate of about 24 per year. Work has been sponsored by CNPq, GSK, AstraZeneca, Organon, Schering-Plough, the EPSRC, STFC, CCLRC, WESTChem and the University of Strathclyde.
Working with the Mulvey group led me to appreciate that the elegant simplicity of the fundamental properties of s-block metals could lead to beautifully complex structures of materials with intrinsic usefulness.
My highlight from this body of work was our success in changing the reactivity profiles of amide and alkyl bases by using hetero-metallic mixes of group 1 and group 2 metals (or Zn) in place of the commonly using single metal, or mixed group 1 metal, reagents.
Recent work describes selective metadeprotonation of toluene, tetra-deprotonation of ferrocene, ruthenocene and osmocene and mono-deprotonation of bis-benzene chromium as well as the trapping of an intermediate in the alkylation of benzophenone and the functionalisation of a range of heterocycles such as THF, furan and pyrazine.
For examples see, Science, 2014, 346, 834-837 & 2009, 326, 706-708;Nature Chem. 2010, 2, 588; Science Adv. 2017, 3, e1700832 & J. Amer. Chem. Soc. 2011, 133, 13706 & 2005, 127, 13106 & 2005, 127, 6184 & 2005, 127, 6920 & 2004, 126, 11612; Chem. Sci. 2013, 4, 1895 & 4259; PNAS 2010, 107, 5294; Chem. Eur. J. 2019. 25, 14728 & 2011, 17, 8333 & 3364; Angew. Chem. 2019, 58 12291 & 12898 & 2017, 56, 1036 & 2016, 55, 16145 & 13147 & 2015, 54, 14075 & 2013, 52, 7190, & 2010, 49, 9388 & 2010, 49, 3185 & 2007, 46, 1105 & 2005, 44, 69; Chem. Commun. 2017, 53, 324 & 3653 & 2016, 52, 12199 & 2013, 49, 8659 & 2012, 48, 5265 & 2012, 48,2011, 388 & 2010, 2319 & 2008, 2638 & 2007, 2864 & 2006, 417 & 3208.
After much moaning, Rab has even lowered himself to allowing Transition Metals into the reagents. See for example Angew. Chem. 2009, 48, 3317.
Dyes and Pigments
The above work armed me with a newfound respect for all things alkaline – but also with a healthy distrust of systems that burst into flames every couple of days. Whilst looking around for a simple (and water stable) application for knowledge of s-block structures I was introduced to dye and pigment chemistry by Prof. W. Ewen Smith. Many so called organic colourants are in fact s-block metal complexes (indeed MOFs to the initiated).
We have shown that common sulphonated azo dyes have fascinating supramolecular structures ranging from solvent-seperated ion-pairs through simple chains, ladders and sheets to complex 3D networks. Building up a database of over 100 structures of simple salts of these dyes allows definitive predictions about their structures to be made - mostly based upon the metal cation used and the position of the sulfonate group. This work has been extended to lake pigments, including a series of structures of Lithol Red. This latter is of special interest due to its (mis?)use by the artist Rothko. (See, Chem. Eur. J. 2012, 18, 3064 & 2009, 15, 9494 &2004, 10, 4606; Inorg. Chem. 2006, 45, 2965; Angew. Chem. 2000, 112, 652; e-Preservation Sci. 2010, 7, 147. For work on other colourant systems see Chem. Commun. 2015, 51, 1143 and Cryst. Growth Des., 2014, 14, 4849.)
The hope in this type of work is always that you can correlate structure to some useful physical property, but typically not enough structural information is available to make any useful predictions.
Now there is no excuse. Modern crystallography, with fast diffractometers, synchrotron sources and structure solutions from powder diffraction data enables whole families of closely related structures to be elucidated, where previously only a few "important" compounds would be studied.
We've taken the approach of building structural databases of many related "boring" structures and gleaning information by studying patterns in the data as a whole as opposed to describing one structure at a time. (Mony a miekel maks a muckle, as my old granny would have said. Ask your local Scottish person if you want a translation.)
This is what has allowed us to link simple characteristics of the metals (e.g. electronegativity) or dyes (e.g. SO3 position) to solid-state structural type and this in turn is linked to properties of interest to manufacturers (solubility, morphology).
A similar methodology has allowed us to examine organic electronic materials, mostly BTBT-types (with Yves Geerts) and DPP-types (with Callum McHugh). Work published to date includes Adv. Mat. 2019, 1902407 & 2016, 28, 7106 & 2015, 27, 3066; ACS Appl. Mater. Interfaces 2015, 7, 1868; J. Mat. Chem. C 2016, 4, 7106; Cryst. Growth Des. 2016, 16, 2371.
We have also applied the mini-structural database idea that worked so well with dyes to pharmaceuticals.
The pharmacy industry calls this sort of thing salt-selection and they seem to have more money than the colourants chemists, so we've upped-sticks and jumped ship. Special thanks must go here to AstraZeneca and Schering-Plough who initiated this mercenary behaviour.
It’s early as yet, but the structures are just as interesting, the links from structure to properties such as aqueous solubility, density and melting point are looking strong and I feel good about looking at socially useful materials. Some aspects of this work can be seen in Cryst. Growth & Des. 2017, 17, 3277 & 2011, 11, 1318 & 1821. See also Cryst. Growth & Des 2014 14, 6508 & 2013, 13, 5121 and Acta Cryst B 2012, 68, 453.
It would be nice to see some pretty colours again though, so any dye manufacturers with a few pounds to spare should feel free to call…
I am also interested in public engagement in science and give a mean talk on scientific understanding, mis-understanding and downright stupidity. Suitable for 15 to 90 year olds with or without a chemistry background.
Finally, we (of course) offer a commercial single crystal diffraction service to industry. If you want to know more about this or any of the other activities above then feel free to get in touch.
Expertise related to UN Sustainable Development Goals
In 2015, UN member states agreed to 17 global Sustainable Development Goals (SDGs) to end poverty, protect the planet and ensure prosperity for all. This person’s work contributes towards the following SDG(s):
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- 3 Finished
11/05/15 → 1/05/19
Project: Research - Studentship
Activation-deactivation of inter-peptide bond in fluoro-N-(2-hydroxy-5-methyl phenyl)benzamide isomers, induced by the position of the halogen atom in the benzene ringMoreno-Fuquen, R., Mariño-Ocampo, N., Tenorio, J. C., Ellena, J. & Kennedy, A. R., 29 Jul 2022, In: Molbank. 2022, 3, 12 p., M1416.
Research output: Contribution to journal › Article › peer-reviewOpen AccessFile
Catalytic hydrophosphination of alkynes using structurally diverse sodium diphenylphosphide donor complexesWhitelaw, M. T., Banerjee, S., Kennedy, A. R., van Teijlingen, A., Tuttle, T. & Mulvey, R. E., 20 Jul 2022, In: Cell Reports Physical Science. 3, 7, 100942.
Research output: Contribution to journal › Article › peer-reviewOpen AccessFile1 Downloads (Pure)
Data for: "Rubidium and caesium aluminyls: synthesis, structures, and reactivity in C-H bond activation of benzene"
Banerjee, S. (Contributor), MacDonald, P. A. (Contributor), Kennedy, A. (Contributor), van Teijlingen, A. (Contributor), Robertson, S. (Contributor), Tuttle, T. (Contributor) & Mulvey, R. (Creator), University of Strathclyde, 1 Aug 2022