Professor Duncan Bruce

01904 324085
Email: duncan.bruce@york.ac.uk

Liquid Crystals and Materials Chemistry

Career Summary

Duncan is a Cumbrian who graduated from the University of Liverpool in 1981 and remained there for his PhD under the supervision of David Cole-Hamilton. His thesis concerned phosphine complexes of PtII and RhI as potential photocatalysts for the decomposition of water. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and in 1986 was awarded a Royal Society Warren Research Fellowship, which he held there until 1991. He was then appointed Lecturer in Chemistry and was promoted to Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following Exeter's disastrous closure of Chemistry in 2005, Duncan took up his present position as Professor of Materials Chemistry in York. 

He served as President of the Royal Society of Chemistry Materials Division from 2006-2009, Chair of the British Liquid Crystal Society from 2009-2011 and is currently an elected member of RSC Council and Chair of its Audit Committee.

His work has been recognised by various awards including British Liquid Crystal Society's first Young Scientist prize (1990) and the RSC's Peter Day Award (2014), Tilden Prize (2010), Corday-Morgan Medal and Prize (1996) and Sir Edward Frankland Fellowship (1994/95). He has held visiting positions in Argentina, Australia, Chile, France, Japan, Italy and Taiwan.

 

Research Interests

The group has a range of interests, a common factor of all being liquid crystals. Examples of current projects include:

Halogen-bonded Liquid Crystals and Co-crystals: non-mesomorphic precursors bind to one another via a halogen bond between an electron-poor iodide and an electron-rich nitrogen. The resulting complexes are found to have liquid crystal properties.

  Reproduced by kind permission of the ACS

liquid crystals         Structures of halogen bonded liquid crystals

 

A full and systematic study of some 90 halogen-bonded liquid crystals was published in collaboration with the Milan group, while more recently we have described liquid crystals arising from the complexation of molecular iodine to alkoxystilbazoles.

stilbazole iodostilbene complex

 

stilbazole iodine complex 1

 

stilbazole iodine complex 2

 

Led by Peter Karadakov, we have undertaken theoretical studies of some aspects of halogen bonding, including a study of the weak attractive interactions between halogen bond donors and rare gases.

 

halogen bonding orbital diagram

 Reproduced by kind permission of the ACS

In a detailed study of co-crystals of 4-halotetrafluorophenol with secondary and tertiary amines, it was found that the phenate anion in the crystal had a delocalised structure meaning that the phenolic oxygen formed a double bond to the ring carbon (borne out by calculation at the MP2 level of theory). The two sp2 orbitals then formed either two hydrogen bonds or one halogen and one hydrogen bond, depending on the number of acidic hydrogen atoms available. Further, in some cases where there were two, in-plane hydrogen bonds to the sp2 orbitals on oxygen, there was, in addition, a halogen bond from a neighbouring iodine to oxygen through the C=O ∏-bond. This study has significance in describing synthetic models for halogen bonding in biological systems.

 phenate amine complex‌ 

oxygen iodine halogen bond phenate amide complex

Luminescent Liquid Crystals for OLED Applications: orthometallated 2-phenylpyridine derivatives of platinum(II) and iridium(III) have desirable photophysical properties as the triplet excited states lead to useful emission owing to spin-orbit coupling between the third-row transition metal and the ligand excited state. Therefore, complexes of this general type are of interest as the emissive component of OLED fabrications as both singlet and triplet states can be harvested.


However, if such complexes can also show liquid crystal properties then additional effects may be realised, for example enhanced carrier mobilities or polarised emission.
We have prepared families of materials which show both triplet emission and liquid crystal properties, based on platinum(II) and iridium (III) and with substantial solution quantum yields. The complexes of the terdentate ligand are of note as the nature of the emissive state can be controlled as a consequence of the liquid crystal nature of the material. Thus, emission from the monomer state can be obtained and reversible interchanged with emission from the excimer.‌

phenyl pyridine Pt complex 1phenyl pyridine Pt complex 2 phenyl pyridine Ir complex

 

  

Nanoparticle-doped, Nanostructured, Mesoporous Silicates: can be prepared by templating silica formation around the liquid crystal phase of a metallosurfactant using a sol-gel methodology. We have shown that surfactant ruthenium bipyridine complexes can do this and that the RuO2-doped materials formed are good oxidation catalysts and very good hydrogenation catalysts when the particles are reduced to Ru0. However, the Ru surfactants appear to be fairly unique as many other metallosurfactants that we synthesised proved to be ineffective templating agents. Therefore we sought an alternative approach.

What we did was to use the mesophase of neutral, ethylene oxide surfactants (e.g. C12EO8) who hexagonal phase was prepared with an aqueous solution of the Group 1 metal salt of an inert metallate anion (e.g. K2[PtCl4] or the Group 1 salt of an EDTA complex (e.g. Na[Fe(EDTA)]). Sol-gel condensation of Si(OMe)4 followed by calcination led to silicates containing a dispersion of metal nanoparticles. Porous silicates containing bimetallic nanoparticles were also made in this way and the approach has been extended to SBA-15

More recently, with Wilson and Lee (Aston) we have exploited these approaches and the combination of meso- and micro-porosity offered by SBA-16 and KIT-6 to demonstrate a range of palladium-catalysed reactions.

Structure and electron-microsope image of Nanoparticle-doped, Nanostructured, Mesoporous Silicates
Ir-containing silicates prepared by the new methodology. Reproduced by kind permission of the Royal Society of Chemistry.

 

 

Recent References

Halogen Bonding:

A. Takemura, L. J. McAllister, S. Hart, N. E. Pridmore, P. B. Karadakov, A. C. Whitwood and D. W. Bruce, Chem. Eur. J., 2014. DOI: 10.1002/chem.201402128.

L. J. McAllister, C. Präsang, J. P.-W. Wong, R. J. Thatcher, A. C. Whitwood, B. Donnio, P. O'Brien, P. B. Karadakov and D. W. Bruce, Chem. Commun., 2013, 49, 3946.

L. J. McAllister, D. W. Bruce and P. B. Karadakov, J. Phys. Chem A, 2012, 116, 10621.

D. W. Bruce,P. Metrangolo, F. Meyer, T. Pilati, C. Präsang, G. Resnati, G. Terraneo, S. G. Wainwright and A. C. Whitwood, Chem. Eur. J., 2010, 16, 9511.

Luminescent Liquid Crystals:

M. Spencer, A. Santoro, A. Díez, P. R. Murray, G. R. Freeman, J. Torroba, A. C. Whitwood, L. J. Yellowlees, J. A. G. Williams and D. W. Bruce, Dalton Trans., 2012, 41, 14244.

A. M. Prokhorov, A. Santoro, J. A. G. Williams and D. W. Bruce, Angew. Chem. Int. Ed., 2012, 51, 95.

A. Santoro, A. M. Prokhorov, V. N. Kozhevnikov, A. C. Whitwood, B. Donnio, J. A. G. Williams and D. W. Bruce, J. Am. Chem. Soc., 2011, 133, 5248.

Mesoporous Silicas:

C. M. A. Parlett, P. Keshwalla, S. G. Wainwright, D. W. Bruce, N. S. Hondow, K. Wilson and A. F. Lee, ACS Catal., 2013, 3, 2122.

S. G. Wainwright, C. M. A. Parlett, R. A. Blackley, W. Zhou, A. F. Lee, K. Wilson and D. W. Bruce, Micropor. Mesopor. Mat., 2013, 172, 112.

C. M. A. Parlett, D. W. Bruce, N. S. Hondow, A. F. Lee and K. Wilson, ACS Catal., 2011, 1, 636.