At the International Conference on Raman Spectroscopy
Great to see so many Gordon group students and graduates at the recent ICORS meeting in Rome.
Here in the photo we have Carlie Watt (Cushla’s student), Dr Cushla McGoverin (Auckland), Keith, Amir Sohail, Karlis Berzins (Copenhagen), Sam Harris, Clare Strachan (Helsinki), Peter Remoto and Jervee Punzalan
Summer scholarship project 1. Spinning long-lived excited states (JDC/KCG)
Kia ora
One of our funded summer scholarships available with the group.
Summer scholarship project 1. Spinning long-lived excited states (JDC/KCG)
Contact: keith.gordon@otago.ac.nz or jcrowley@chemistry.otago.ac.nz
Account code: 121.968.01.P.FE
10 weeks over the summer – dates negotiable
Molecular excited states are the key species in many renewable technologies; they are pivotal to the operation of solar cells1-3, organic light emitting diodes4, 5 and in photocatalysts.6, 7 The critical parameters for these excited states are:
1. The efficiency of population of the desired excited state – that is how many photons get you the state required (the quantum yield)?
2. The energy of the active excited state
3. The lifetime of this excited state
In molecular systems there is a design tension between the creation of long-lived excited states (which are often triplet states) and the population of such states – long-lived triplet states have low spin-orbit coupling and thus their population, either by direct photoexcitation or, through subsequent excited state relaxation, is low. If spin-orbit coupling is increased, by using a metal complex, the efficiency of triplet state population is improved but this comes at the cost of decreasing the lifetime. A strategy for circumventing the undesirable effects of spin-orbit coupling is to isolate the triplet excited state away from the metal after intersystem crossing has occurred. We have shown that it is possible to make molecules that can access long-lived ligand-based triplet states called intraligand charge-transfer states.8-12 We will test this by systematic alteration of these states using earth abundant metals (such as Zn, Cu, Fe) coupled with systematic tuning of the ligand.13-20 Ultimately, this could provide materials that possess readily tuneable long-lived excited states using earth abundant metals.
- Kwok, E. C.-H.; Chan, M.-Y.; Wong, K. M.-C.; Lam, W. H.; Yam, V. W.-W., Functionalized Alkynylplatinum(II) Polypyridyl Complexes for Use as Sensitizers in Dye-Sensitized Solar Cells. Chemistry – A European Journal 2010, 16 (40), 12244-12254.
- Kinoshita, T.; Dy, J. T.; Uchida, S.; Kubo, T.; Segawa, H., Wideband dye-sensitized solar cells employing a phosphine-coordinated ruthenium sensitizer. Nature Photonics 2013, 7 (7), 535-539.
- Grätzel, M., Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells. Inorganic Chemistry 2005, 44 (20), 6841-6851.
- Noda, H.; Nakanotani, H.; Adachi, C., Excited state engineering for efficient reverse intersystem crossing. Science Advances 2018, 4 (6), eaao6910.
- Bergmann, L.; Hedley, G. J.; Baumann, T.; Bräse, S.; Samuel, I. D. W., Direct observation of intersystem crossing in a thermally activated delayed fluorescence copper complex in the solid state. Science Advances 2016, 2 (1), e1500889.
- Proppe, A. H.; Li, Y. G. C.; Aspuru-Guzik, A.; Berlinguette, C. P.; Chang, C. J.; Cogdell, R.; Doyle, A. G.; Flick, J.; Gabor, N. M.; van Grondelle, R.; Hammes-Schiffer, S.; Jaffer, S. A.; Kelley, S. O.; Leclerc, M.; Leo, K.; Mallouk, T. E.; Narang, P.; Schlau-Cohen, G. S.; Scholes, G. D.; Vojvodic, A.; Yam, V. W. W.; Yang, J. Y.; Sargent, E. H., Bioinspiration in light harvesting and catalysis. Nat. Rev. Mater. 2020, 5 (11), 828-846.
- Förster, C.; Heinze, K., Photophysics and photochemistry with Earth-abundant metals – fundamentals and concepts. Chemical Society Reviews 2020.
- Shillito, G. E.; Preston, D.; Traber, P.; Steinmetzer, J.; McAdam, C. J.; Crowley, J. D.; Wagner, P.; Kupfer, S.; Gordon, K. C., Excited-State Switching Frustrates the Tuning of Properties in Triphenylamine-Donor-Ligand Rhenium(I) and Platinum(II) Complexes. Inorganic Chemistry 2020, 59 (10), 6736-6746.
- Shillito, G. E.; Hall, T. B. J.; Preston, D.; Traber, P.; Wu, L. J.; Reynolds, K. E. A.; Horvath, R.; Sun, X. Z.; Lucas, N. T.; Crowley, J. D.; George, M. W.; Kupfer, S.; Gordon, K. C., Dramatic Alteration of (ILCT)-I-3 Lifetimes Using Ancillary Ligands in Re(L)(CO)(3)(phen-TPA) (n+) Complexes: An Integrated Spectroscopic and Theoretical Study. Journal of the American Chemical Society 2018, 140 (13), 4534-4542.
- Barnsley, J. E.; Findlay, J. A.; Shillito, G. E.; Pelet, W. S.; Scottwell, S. O.; McIntyre, S. M.; Tay, E. J.; Gordon, K. C.; Crowley, J. D., Long-lived MLCT states for Ru(ii) complexes of ferrocene-appended 2,2 ‘-bipyridines. Dalton Transactions 2019, 48 (41), 15713-15722.
- Larsen, C. B.; van der Salm, H.; Clark, C. A.; Elliott, A. B. S.; Fraser, M. G.; Horvath, R.; Lucas, N. T.; Sun, X. Z.; George, M. W.; Gordon, K. C., Intraligand Charge-Transfer Excited States in Re(I) Complexes with Donor-Substituted Dipyridophenazine Ligands. Inorganic Chemistry 2014, 53 (3), 1339-1354.
- Shillito, G. E.; Larsen, C. B.; McLay, J. R. W.; Lucas, N. T.; Gordon, K. C., Effect of Bridge Alteration on Ground- and Excited-State Properties of Ruthenium(II) Complexes with Electron-Donor-Substituted Dipyrido 3,2-a:2 ‘,3 ‘-c phenazine Ligands. Inorganic Chemistry 2016, 55 (21), 11170-11184.
- Preston, D.; Barnsley, J. E.; Gordon, K. C.; Crowley, J. D., Controlled Formation of Heteroleptic Pd-2(L-a)(2)(L-b)(2) (4+) Cages. Journal of the American Chemical Society 2016, 138 (33), 10578-10585.
- Preston, D.; Findlay, J. A.; Crowley, J. D., Recognition Properties and Self-assembly of Planar M(2-pyridyl-1,2,3-triazole)(2) (2+) Metallo-ligands. Chemistry-an Asian Journal 2019, 14 (8), 1136-1142.
- Mapley, J. I.; Ross, D. A. W.; McAdam, C. J.; Gordon, K. C.; Crowley, J. D., Triphenylamine-substituted 2-pyridyl-1,2,3-triazole copper(I) complexes: an experimental and computational investigation. Journal of Coordination Chemistry 2019, 72 (8), 1378-1394.
- Preston, D.; Sutton, J. J.; Gordon, K. C.; Crowley, J. D., A Nona-nuclear Heterometallic Pd3Pt6 “Donut”-Shaped Cage: Molecular Recognition and Photocatalysis. Angewandte Chemie-International Edition 2018, 57 (28), 8659-8663.
- Findlay, J. A.; McAdam, C. J.; Sutton, J. J.; Preston, D.; Gordon, K. C.; Crowley, J. D., Metallosupramolecular Architectures Formed with Ferrocene-Linked Bis-Bidentate Ligands: Synthesis, Structures, and Electrochemical Studies. Inorganic Chemistry 2018, 57 (7), 3602-3614.
- Vasdev, R. A. S.; Preston, D.; Crowley, J. D., Functional metallosupramolecular architectures using 1,2,3-triazole ligands: it’s as easy as 1,2,3 “click”. Dalton Transactions 2017, 46 (8), 2402-2414.
- Barnsley, J. E.; Shillito, G. E.; Larsen, C. B.; van der Salm, H.; Horvath, R.; Sun, X. Z.; Wu, X.; George, M. W.; Lucas, N. T.; Gordon, K. C., Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime. Inorganic Chemistry 2019, 58 (15), 9785-9795.
- Huff, G. S.; Lo, W. K. C.; Horvath, R.; Turner, J. O.; Sun, X. Z.; Weal, G. R.; Davidson, H. J.; Kennedy, A. D. W.; McAdam, C. J.; Crowley, J. D.; George, M. W.; Gordon, K. C., Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes. Inorganic Chemistry 2016, 55 (23), 12238-12253.
Keith’s work highlighted by Riddet and Research.com
Keith’s work was highlighted recently by the Riddet Inst. where he works with Prof. Indra Owati and others and PhD student Jervee Punzalan.
Keith attends PCCP symposium and editorial board meeting
Keith recently attended the 25th anniversary PCCP symposium and editorial board meeting in Amsterdam. The meeting was hosted at Vrije Universiteit Amsterdam. Keith presented a poster on low frequency Raman spectroscopy and chaired one of the sessions.
Catching with ex group members at the NIR conference
A photo of Jervee with past graduates of the group. Left to right: Jervee Punzalan, Dr Chima Robert, Dr Cushla McGoverin and Dr Samanali Garagoda Arachchige
Congratulations Jervee on winning conference support
Jervee Punzalan has been awarded the NZNIRSS Student Award for the 20th ANISG/NZNIRSS Conference in Christchurch, taking place from April 8th to 11th, 2024.
The award acknowledges Jervee‘s work for the near-infrared spectroscopy research and provides NZD 500 towards conference expenses. This will allow her to engage with experts, present research findings, and network with peers.
Listen to Peter’s cool podcast
Peter Remoto talking about his experiences at Uni and in research. Worth watching to the end; very interesting talk.
Great chat!
Episode 107 – When a passion turns to a PhD (youtube.com)
New paper in Nano Today
Congratulations to Keith Gordon and collaborators from Shanghai on their recent paper in Nano Today. The paper entitled “Functional separator materials of sodium-ion batteries: Grand challenges and industry perspectives.” (Nano Today 2024, 55, 102175. DOI: https://doi.org/10.1016/j.nantod.2024.102175) describes the issues around battery membranes and area that spatially offset Raman spectroscopy may be able to play a role in understanding.
Invited talk at the Australia New Zealand Ultrafast meeting
Keith gave an invited talk at the recent Australia New Zealand Ultrafast meeting in Sydney. He talked about “The creation of long-lived excited states through design: a computational and time-resolved experimental study”
PhD opportunities with Marsden grant
PhD positions in Chemistry, University of Otago, New Zealand
Two positions in synthetic inorganic chemistry and one in spectroscopy of inorganic systems
Title
Hydrogen generation with sustainable resources – a combined molecular, computational and engineering approach
Supervisors
Professor James Crowley and Professor Keith Gordon
Description
Hydrogen is an important fuel source and commodity chemical used in a wide range of industrial processes. Unfortunately, almost all the hydrogen produced currently is obtained from the steam reforming process which is both energy intensive and generates carbon dioxide as a by-product. There are already several photocatalytic systems, including bimetallic metal complexes that can efficiently generate hydrogen in this way. However, the current technologies use Noble metals which are expensive and rare. We will use earth abundant transition metals such as iron, cobalt and copper by re-designing the photocatalytic systems. This project is a Marsden funded project involving researchers in Jena, Germany (Profs Kupfer, Shillito and Weigand) and Nottingham, UK (Prof George) The project may involve visits to collaborators in Germany and the UK.
Kindly contact either jcrowley@chemistry.otago.ac.nz or keith.gordon@otago.ac.nz with any questions
Prior experience
The projects involve the synthesis of new metal complexes and their study using spectroscopy and computational chemistry. Two of the researchers will focus more on synthesis with the third undertaking computational studies and spectroscopic measurements including transient spectroscopy. Some overlap of expertise and interest is welcome. Experience in any of these areas is useful.
Stipend
NZD 35,000 per annum plus fees.
Application
As part of your application package, kindly include:
– CV (including 2-3 referee information)
– Cover Letter (this may include: a description of why you want to undertake a PhD; how your previous experiences have prepared you for the research project that you are applying for; what your passions are within or outside of academia)
Applications will be accepted beginning February until the positions are filled.
Kindly contact either jcrowley@chemistry.otago.ac.nz or keith.gordon@otago.ac.nz with any questions
