Prof. Andrew Beeby

Personal web page

(email at andrew.beeby@durham.ac.uk)

Research Interests

My research interests lie in the fields of photochemistry and photophysics. This work encompasses a wide range of related topics, including the determination of fundamental photophysical parameters, the identification of intermediate species and their kinetic behaviour and the characterisation of a reactions end-products. It is only by having a detailed understanding of all these factors that we can design chemical systems in which we have control over the direction and outcome of photochemical reactions. This comprehensive approach is applied to the study of a number of photo-induced reactions, such as energy transfer, electron transfer and isomerisation. These processes are studied in a range of chemical systems including commercially important materials, e.g. electroluminescent materials, molecular probes containing lanthanide ions, sunscreens, as well as those of more fundamental scientific interest.

The group is well equipped to carry out photophysical measurements. We routinely study samples in both solution and solid states, including homogeneous and inhomogeneous thin films. We can study samples in inert atmospheres and record data over a wide temperature range. In addition to conventional steady-state UV-vis-NIR absorption and fluorescence spectrometers we also have luminescence and Raman imaging microscopes, ns-laser flash photolysis, and fluorescence lifetime spectrometers. We always welcome enquiries from groups that would like to collaborate on any measurements.

Pigments in Medieval Manuscripts

Identifying the materials used in medieval illuminated manuscripts gives us an insight into the techniques and skills of the scribes and illuminators, as well as the sometimes complex trade routes of the times. The challenge is to be able to identify materials on a delicate sheet of parchment, typically a folio of a bound manuscript that does not open readily, without contact, sampling or causing any damage. Ideally the technique should give an unequivocal identification of pigments with high spatial resolution and selectivity: a challenge indeed! At Durham we use Raman spectroscopy combined with hyperspectral imaging and diffuse reflectance spectroscopy to achieve this. Are currently studying the pigments used in manuscripts produced in the British Isles and northern Europe between the 7^th and 15^th centuries.

The example shown is from Libellus de Exordio atque Procursu istius, hoc est Dunelmensis, Ecclesie (The Little Book on the Origins and Progress of this Church, that is of Durham) written by Symeon ca. 1105, and resides normally at Durham, University Library, Cosin V.II.6. The spectrum below show the presence of lapis lazuli which came from what is now Afghanistan.

Oligoaryleneethynenes

These highly luminescent compounds are currently the subject of intense attention as potential 'molecular wires and switches' and as emissive layers for organic LED's. In collaboration with colleagues at Durham we have been using optical spectroscopies to investigate the role of structure, particularly conformation, upon the emission and material properties of the compounds. We are particularly interested in the electronic structure and bond-order of the ground and excited states and the role of conformation upon these parameters.

Organometallic Complexes as Light Emitting Materials

In the near future it is expected that conventional displays, based upon cathode-ray tubes, will be replaced by new technologies utilising thin-film electroluminecent materials. Devices based upon organic materials rely upon the recombination of holes and electrons that are injected into the material producing excited states, known as excitons, which can be either triplet or singlet character. In conventional materials based upon conjugated polymers only the singlet state excitons can emit light, and triplet excitons, are effectively wasted energy. Our interest lies in the use of organometallic complexes that are capable of harvesting both singlet and triplet excitons to produce light output and includes both the synthesis of new materials and the study of their spectroscopic properties.

The Luminescence of Complexed Lanthanide(III) Ions

We are studying the fundamental photophysical properties of lanthanide ions, including the investigation of the pathways of energy transfer from organic chromophores to the metal ions. Although the properties of terbium and europium have been extensively studied the photophysical behaviour of many other luminescent lanthanide ions in solution have been somewhat neglected for various reasons. We are investigating systems based upon neodymium, ytterbium and erbium in various media and have observed interesting isotope and ligand effects. This work is technically challenging due to the fact that the emission is often very weak, short lived and in the near infra-red spectral region.

Excitation and emission matrix obtained from 1,4-bis(phenylethynyl)benzene in cyclohexane at 298K This spectrum shows that the emission spectrum is independent of the excitation wavelength, indicating that under these conditions the relaxation of excited state conformers occurs very rapidly.²

References

• A. Beeby, K. S. Findlay, P.J. Low, T.B. Marder, P. Matousek, A.W. Parker, S.R. Rutter, M. Towrie, Chem Commun., 2003, 2406.
• A. Beeby, K. Findlay, P.J. Low, T.B. Marder, J. Am. Chem. Soc., 2002, 124, 8280.
• A. Beeby, S.L. Bettington, I.D.W.Samuel and Z.Wang, J. Mater. Chem., 2002, 13, 80.
• A. Beeby, S. Bettington, I.J.S. Fairlamb, A.E. Goeta, A.R. Kapdi, E.H. Niemela and A.L. Thompson, New J. Chem., 2004, 600-605.
• A. Beeby, A.E. Jones, Photochem. Photobiol., 2000, 72, 10.
• A. Beeby, S. FitzGerald and C.F. Stanley, J. Chem. Soc. Perkin Trans. 2., 2001, 1978.

Research Groups

Department of Chemistry

• Functional Molecules and Materials

Research Projects

Department of History

• British Medieval Illuminators’ Pigments: A Scientific and Cultural Study

Research Interests

• Multispectral imaging
• Photochemistry
• Photophysics
• Pigments of medieval manuscripts
• Spectroscopy
• Time-resolved spectorscopy

Publications

Journal Article

• Suhling, Klaus, Hirvonen, Liisa M., Becker, Wolfgang, Smietana, Stefan, Netz, Holger, Milnes, James, Conneely, Thomas, Marois, Alix Le, Jagutzki, Ottmar, Festy, Fred, Petrášek, Zdeněk & Beeby, Andrew (2019). Wide-field time-correlated single photon counting-based fluorescence lifetime imaging microscopy. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 942: 162365.
• Bryden, Francesca, Maruani, Antoine, Rodrigues, João M. M., Cheng, Miffy H. Y., Savoie, Huguette, Beeby, Andrew, Chudasama, Vijay & Boyle, Ross W. (2018). Assembly of High-Potency Photosensitizer–Antibody Conjugates through Application of Dendron Multiplier Technology. Bioconjugate Chemistry 29(1): 176-181.
• Davidson, Ross J., Milan, David C., Al-Owaedi, Oday A., Ismael, Ali K., Nichols, Richard J., Higgins, Simon J., Lambert, Colin J., Yufit, Dmitry S. & Beeby, Andrew (2018). Conductance of ‘bare-bones’ tripodal molecular wires. RSC Advances 8(42): 23585-23590.
• Davidson, Ross, Hsu, Yu-Ting, Griffiths, Gareth C., Li, Chenfei, Yufit, Dmitry, Pal, Robert & Beeby, Andrew (2018). Highly Linearized Twisted Iridium(III) Complexes. Inorganic Chemistry 57(22): 14450-14462.
• Batsanov, Stepan S., Osavchuk, Alexander N., Naumov, Stepan P., Gavrilkin, Sergey M., Leskov, Anatoly S., Mendis, Budhika G., Beeby, Andrew & Batsanov, Andrei S. (2018). Novel synthesis and properties of hydrogen-free detonation nanodiamond. Materials Chemistry and Physics 216: 120-129.
• Marucci, G., Beeby, A., Parker, A. W. & Nicholson, C. E. (2018). Raman spectroscopic library of medieval pigments collected with five different wavelengths for investigation of illuminated manuscripts. Analytical Methods 10(10): 1219-1236.
• Beeby, Andrew, Garner, Louise, Howell, David & Nicholson, Catherine E. (2018). There’s More to Reflectance Spectroscopy Than Lux. Journal of the Institute of Conservation 41(2): 142-153.
• Davidson, Ross, Hsu, Yu-Ting, Bhagani, Chandni, Yufit, Dmitry & Beeby, Andrew (2017). Exploring the Chemistry and Photophysics of Substituted Picolinates Positional Isomers in Iridium(III) Bisphenylpyridine Complexes. Organometallics 36(15): 2727-2735.
• Mulholland, R., Howell, D., Beeby, A., Nicholson, C. E. & Domoney, K. (2017). Identifying eighteenth century pigments at the Bodleian library using in situ Raman spectroscopy, XRF and hyperspectral imaging. Heritage Science 5(1): 43.
• Roy, Khokan, Kayal, Surajit, Ariese, Freek, Beeby, Andrew & Umapathy, Siva (2017). Mode specific excited state dynamics study of bis(phenylethynyl)benzene from ultrafast Raman loss spectroscopy. The Journal of Chemical Physics 146(6): 064303.
• Štefančič, Aleš, Klupp, Gyöngyi, Knaflič, Tilen, Yufit, Dmitry S., Tavčar, Gašper, Potočnik, Anton, Beeby, Andrew & Arčon, Denis (2017). Triphenylide-Based Molecular Solid—A New Candidate for a Quantum Spin-Liquid Compound. The Journal of Physical Chemistry C 121(27): 14864-14871.
• Roy, Khokan, Kayal, Surajit, Kumar, Venkatraman Ravi, Beeby, Andrew, Ariese, Freek & Umapathy, Siva (2017). Understanding Ultrafast Dynamics of Conformation Specific Photo-Excitation: A Femtosecond Transient Absorption and Ultrafast Raman Loss Study. The Journal of Physical Chemistry 121(35): 6538-6546.
• Liang, Jinghong, Smith, Robert E.G., Vezzoli, Andrea, Xie, Liqiang, Milan, David C., Davidson, Ross, Beeby, Andrew, Low, Paul J., Higgins, Simon J., Mao, Bingwei & Nichols, Richard J. (2016). Electrochemically grafted single molecule junctions exploiting a chemical protection strategy. Electrochimica Acta 220: 436-443.
• Ishida, Hitoshi, Bünzli, Jean-Claude & Beeby, Andrew (2016). Guidelines for measurement of luminescence spectra and quantum yields of inorganic and organometallic compounds in solution and solid state (IUPAC Technical Report). Pure and Applied Chemistry 88(7): 701-711.
• Zhang, W., Gan, S., Vezzoli, A., Davidson, R.J., Milan, D.C., Luzyanin, K.V., Higgins, S.J. Nichols, R.J., Beeby, A., Low, P.J., Li, B. & Niu, L. (2016). Single-Molecule Conductance of Viologen–Cucurbit[8]uril Host–Guest Complexes. ACS Nano 10(5): 5212-5220.
• Davidson, Ross, Hsu, Yu-Ting, Batchelor, Thomas, Yufit, Dimitry & Beeby, Andrew (2016). The use of organolithium reagents for the synthesis of 4-aryl-2-phenylpyridines and their corresponding iridium(III)complexes. Dalton Transactions 45(28): 11496.
• Davidson, R.J., Wilson, L.E., Duckworth, A.R., Yufit, D.S., Beeby, A. & Low, P.J. (2015). Alkyne substituted mononuclear photocatalysts based on [RuCl(bpy)(tpy)](+). Dalton Transactions 44(25): 11368-11379.
• Amara, Z., Bellamy, J.F.B., Horvath, R., Miller, S.J., Beeby, A., Burgard, A., Rossen, K., Poliakoff, M. & George, M.W. (2015). Applying green chemistry to the photochemical route to artemisinin. Nature Chemistry 7(6): 489-495.
• Lavado, A.S., Chauhan, V.M., Zen, A.A., Giuntini, F., Jones, D.R.E., Boyle, R.W., Beeby, A., Chan, W.C. & Aylott, J.W. (2015). Controlled intracellular generation of reactive oxygen species in human mesenchymal stem cells using porphyrin conjugated nanoparticles. Nanoscale 7(34): 14525-14531.
• Gluyas, J.B.G., Manici, V., Gückel, S., Vincent, K.B., Yufit, D.S., Howard, J.A.K., Skelton, B.W., Beeby, A., Kaupp, M. & Low, P.J. (2015). Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations. The Journal of Organic Chemistry 80(22): 11501-11512.
• De Ornellas, S., Slattery, J.M., Edkins, R.M., Beeby, A., Baumann, C.G. & Fairlam, I.J.S. (2015). Design and synthesis of fluorescent 7-deazaadenosine nucleosides containing pi-extended diarylacetylene motifs. Organic & Biomolecular Chemistry 13(1): 68-72.
• Stasiuk, Graeme J., Minuzzi, Florencia, Sae-Heng, Myra, Rivas, Charlotte, Juretschke, Hans-Paul, Piemonti, Lorenzo, Allegrini, Peter R., Laurent, Didier, Duckworth, Andrew R., Beeby, Andrew, Rutter, Guy A. & Long, Nicholas J. (2015). Dual-Modal Magnetic Resonance/Fluorescent Zinc Probes for Pancreatic β-Cell Mass Imaging. Chemistry - A European Journal 21(13): 5023-5033.
• Hirvonen, Liisa M., Petrášek, Zdeněk, Beeby, Andrew & Suhling, Klaus (2015). Sub-μs time resolution in wide-field time-correlated single photon counting microscopy obtained from the photon event phosphor decay. New Journal of Physics 17(2): 023032.
• Davidson, R., Liang, J.H., Milan, D.C., Mao, B.W., Nichols, R.J., Higgins, S.J., Yufit, D.S. Beeby, A. & Low, P.J. (2015). Synthesis, Electrochemistry, and Single-Molecule Conductance of Bimetallic 2,3,5,6-Tetra(pyridine-2-yl)pyrazine-Based Complexes. Inorganic Chemistry 54(11): 5487-5494.
• Edkins R.M., Probert, M.R., Robertson, C.M., Howard, J.A.K., Beeby, A. & Robertson C.M. (2014). Photocrystallisation of the 2C-2'C dimer of a triphenylimidazolyl radical. RSC Advances 4(11): 5351-5356.
• S.J. Greaves, E.L. Flynn, E.L. Futcher, E. Wrede, D. Lydon, P.J. Low, S. Rutter & A. Beeby (2006). Cavity ring-down spectroscopy of the torsional motions of 1,4-bis(phenylethynyl)benzene. Journal of Physical Chemistry A 110(6): 2114-2121.
• Batsanov, A.S., Collings, J.C., Ward, R.M., Goeta, A.E., Porres, L., Beeby, A., Howard, J.A.K., Steed, J.W. & Marder, T.B. (2006). Crystal engineering with ethynylbenzenes Part 2. Structures of 4-trimethylsilylethynyl-N,N-dimethylaniline, and 4-ethynyl-N,N-dimethylaniline with Z '=12 and a single-crystal to single-crystal phase transition at 122.5 +/- 2 K. CrystEngComm 8: 622-628.
• Palsson, L.O., Vaughan, H.L., Smith, A., Szablewski, M., Cross, G.H., Roberts, T., Masutani, A., Yasuda, A., Beeby, A. & Bloor, D. (2006). Guest-host interactions between dichroic dyes and anisotropic hosts. Journal of luminescence 117(1): 113-122.
• Khairul, W.M., Porres, L., Albesa-Jove, D., Senn, M.S., Jones, M., Lydon, D.P., Howard, J.A.K., Beeby, A., Marder, T.B. & Low, P.J. (2006). Metal cluster terminated "molecular wires". Journal of cluster science 17(1): 65-85.
• V.A. Azov, A. Beeby, M. Cacciarini, A.G. Cheetham, F. Diederich, M. Frei, J.K. Gimzewski, V. Gramlich, B. Hecht, B. Jaun, T. Latychevskaia, A. Lieb, Y. Lill, F. Marotti, A. Schlegel, R.R. Schlittler, P.J. Skinner, P. Seiler & Y. Yamakoshi (2006). Resorcin 4 arene cavitand-based molecular switches. Advanced functional materials 16(2): 147-156.
• Barker, C.A., Findlay, K.S., Bettington, S., Batsanov, A.S., Perepichka, I.F., Bryce, M.R. & Beeby, A. (2006). Synthesis of new axially-disubstituted silicon-phthalocyanine derivatives optical and structural characterisation. Tetrahedron 62(40): 9433-9439.
• Zhu, X.J., Ward, R.M., Albesa-Jove, D., Howard, J.A.K., Porres, L., Beeby, A., Low, P.J., Wong, W.K. & Marder, T.B. (2006). Synthesis of new mer,trans-rhodium(III) hydrido-bis(acetylide) complexes: Structure of mer,trans- (PMe3)(3)Rh(C equivalent to C-C6H4-4-NMe2)(2)H. Inorganica chimica acta 359(9): 2859-2863.
• King, S.M., Al-Attar, H.A., Evans, R.J., Congreve, A., Beeby, A. & Monkman, A.R. (2006). The use of substituted iridium complexes in doped polymer electrophosphorescent devices The influence of triplet transfer and other factors on enhancing device performance. Advanced functional materials 16(8): 1043-1050.