{"id":653,"date":"2024-07-09T10:13:54","date_gmt":"2024-07-08T22:13:54","guid":{"rendered":"https:\/\/blogs.otago.ac.nz\/keithgordon\/?p=653"},"modified":"2024-07-09T10:13:54","modified_gmt":"2024-07-08T22:13:54","slug":"summer-scholarship-project-1-spinning-long-lived-excited-states-jdc-kcg","status":"publish","type":"post","link":"https:\/\/blogs.otago.ac.nz\/keithgordon\/summer-scholarship-project-1-spinning-long-lived-excited-states-jdc-kcg\/","title":{"rendered":"Summer scholarship project 1. Spinning long-lived excited states (JDC\/KCG)"},"content":{"rendered":"

Kia ora<\/p>\n

One of our funded summer scholarships available with the group.<\/p>\n

Summer scholarship project 1. Spinning long-lived excited states (JDC\/KCG)<\/strong><\/p>\n

Contact: keith.gordon@otago.ac.nz<\/a> or jcrowley@chemistry.otago.ac.nz<\/a><\/p>\n

Account code: 121.968.01.P.FE<\/p>\n

10 weeks over the summer – dates negotiable<\/p>\n

Molecular excited states are the key species in many renewable technologies; they are pivotal to the operation of solar cells1-3<\/sup>, organic light emitting diodes4, 5<\/sup> and in photocatalysts.6, 7<\/sup> The critical parameters for these excited states are:<\/p>\n

1.\u00a0 The efficiency of population of the desired excited state \u2013 that is how many photons get you the state required (the quantum yield)?<\/p>\n

2.\u00a0 The energy of the active excited state<\/p>\n

3.\u00a0 The lifetime of this excited state<\/p>\n

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 \u2013 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<\/sup> 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<\/sup> Ultimately, this could provide materials that possess readily tuneable long-lived excited states using earth abundant metals.<\/p>\n

    \n
  1. Kwok, E. C.-H.; Chan, M.-Y.;\u00a0 Wong, K. M.-C.;\u00a0 Lam, W. H.; Yam, V. W.-W., Functionalized Alkynylplatinum(II) Polypyridyl Complexes for Use as Sensitizers in Dye-Sensitized Solar Cells. Chemistry \u2013 A European Journal <\/em>2010,<\/strong> 16<\/em> (40), 12244-12254.<\/li>\n
  2. Kinoshita, T.; Dy, J. T.;\u00a0 Uchida, S.;\u00a0 Kubo, T.; Segawa, H., Wideband dye-sensitized solar cells employing a phosphine-coordinated ruthenium sensitizer. Nature Photonics <\/em>2013,<\/strong> 7<\/em> (7), 535-539.<\/li>\n
  3. Gr\u00e4tzel, M., Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells. Inorganic Chemistry <\/em>2005,<\/strong> 44<\/em> (20), 6841-6851.<\/li>\n
  4. Noda, H.; Nakanotani, H.; Adachi, C., Excited state engineering for efficient reverse intersystem crossing. Science Advances <\/em>2018,<\/strong> 4<\/em> (6), eaao6910.<\/li>\n
  5. Bergmann, L.; Hedley, G. J.;\u00a0 Baumann, T.;\u00a0 Br\u00e4se, S.; Samuel, I. D. W., Direct observation of intersystem crossing in a thermally activated delayed fluorescence copper complex in the solid state. Science Advances <\/em>2016,<\/strong> 2<\/em> (1), e1500889.<\/li>\n
  6. Proppe, A. H.; Li, Y. G. C.;\u00a0 Aspuru-Guzik, A.;\u00a0 Berlinguette, C. P.;\u00a0 Chang, C. J.;\u00a0 Cogdell, R.;\u00a0 Doyle, A. G.;\u00a0 Flick, J.;\u00a0 Gabor, N. M.;\u00a0 van Grondelle, R.;\u00a0 Hammes-Schiffer, S.;\u00a0 Jaffer, S. A.;\u00a0 Kelley, S. O.;\u00a0 Leclerc, M.;\u00a0 Leo, K.;\u00a0 Mallouk, T. E.;\u00a0 Narang, P.;\u00a0 Schlau-Cohen, G. S.;\u00a0 Scholes, G. D.;\u00a0 Vojvodic, A.;\u00a0 Yam, V. W. W.;\u00a0 Yang, J. Y.; Sargent, E. H., Bioinspiration in light harvesting and catalysis. Nat. Rev. Mater. <\/em>2020,<\/strong> 5<\/em> (11), 828-846.<\/li>\n
  7. F\u00f6rster, C.; Heinze, K., Photophysics and photochemistry with Earth-abundant metals \u2013 fundamentals and concepts. Chemical Society Reviews <\/em>2020<\/strong>.<\/li>\n
  8. Shillito, G. E.; Preston, D.;\u00a0 Traber, P.;\u00a0 Steinmetzer, J.;\u00a0 McAdam, C. J.;\u00a0 Crowley, J. D.;\u00a0 Wagner, P.;\u00a0 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 <\/em>2020,<\/strong> 59<\/em> (10), 6736-6746.<\/li>\n
  9. Shillito, G. E.; Hall, T. B. J.;\u00a0 Preston, D.;\u00a0 Traber, P.;\u00a0 Wu, L. J.;\u00a0 Reynolds, K. E. A.;\u00a0 Horvath, R.;\u00a0 Sun, X. Z.;\u00a0 Lucas, N. T.;\u00a0 Crowley, J. D.;\u00a0 George, M. W.;\u00a0 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 <\/em>2018,<\/strong> 140<\/em> (13), 4534-4542.<\/li>\n
  10. Barnsley, J. E.; Findlay, J. A.;\u00a0 Shillito, G. E.;\u00a0 Pelet, W. S.;\u00a0 Scottwell, S. O.;\u00a0 McIntyre, S. M.;\u00a0 Tay, E. J.;\u00a0 Gordon, K. C.; Crowley, J. D., Long-lived MLCT states for Ru(ii) complexes of ferrocene-appended 2,2 ‘-bipyridines. Dalton Transactions <\/em>2019,<\/strong> 48<\/em> (41), 15713-15722.<\/li>\n
  11. Larsen, C. B.; van der Salm, H.;\u00a0 Clark, C. A.;\u00a0 Elliott, A. B. S.;\u00a0 Fraser, M. G.;\u00a0 Horvath, R.;\u00a0 Lucas, N. T.;\u00a0 Sun, X. Z.;\u00a0 George, M. W.; Gordon, K. C., Intraligand Charge-Transfer Excited States in Re(I) Complexes with Donor-Substituted Dipyridophenazine Ligands. Inorganic Chemistry <\/em>2014,<\/strong> 53<\/em> (3), 1339-1354.<\/li>\n
  12. Shillito, G. E.; Larsen, C. B.;\u00a0 McLay, J. R. W.;\u00a0 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 <\/em>2016,<\/strong> 55<\/em> (21), 11170-11184.<\/li>\n
  13. Preston, D.; Barnsley, J. E.;\u00a0 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 <\/em>2016,<\/strong> 138<\/em> (33), 10578-10585.<\/li>\n
  14. 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 <\/em>2019,<\/strong> 14<\/em> (8), 1136-1142.<\/li>\n
  15. Mapley, J. I.; Ross, D. A. W.;\u00a0 McAdam, C. J.;\u00a0 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 <\/em>2019,<\/strong> 72<\/em> (8), 1378-1394.<\/li>\n
  16. Preston, D.; Sutton, J. J.;\u00a0 Gordon, K. C.; Crowley, J. D., A Nona-nuclear Heterometallic Pd3Pt6 “Donut”-Shaped Cage: Molecular Recognition and Photocatalysis. Angewandte Chemie-International Edition <\/em>2018,<\/strong> 57<\/em> (28), 8659-8663.<\/li>\n
  17. Findlay, J. A.; McAdam, C. J.;\u00a0 Sutton, J. J.;\u00a0 Preston, D.;\u00a0 Gordon, K. C.; Crowley, J. D., Metallosupramolecular Architectures Formed with Ferrocene-Linked Bis-Bidentate Ligands: Synthesis, Structures, and Electrochemical Studies. Inorganic Chemistry <\/em>2018,<\/strong> 57<\/em> (7), 3602-3614.<\/li>\n
  18. 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 <\/em>2017,<\/strong> 46<\/em> (8), 2402-2414.<\/li>\n
  19. Barnsley, J. E.; Shillito, G. E.;\u00a0 Larsen, C. B.;\u00a0 van der Salm, H.;\u00a0 Horvath, R.;\u00a0 Sun, X. Z.;\u00a0 Wu, X.;\u00a0 George, M. W.;\u00a0 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 <\/em>2019,<\/strong> 58<\/em> (15), 9785-9795.<\/li>\n
  20. Huff, G. S.; Lo, W. K. C.;\u00a0 Horvath, R.;\u00a0 Turner, J. O.;\u00a0 Sun, X. Z.;\u00a0 Weal, G. R.;\u00a0 Davidson, H. J.;\u00a0 Kennedy, A. D. W.;\u00a0 McAdam, C. J.;\u00a0 Crowley, J. D.;\u00a0 George, M. W.; Gordon, K. C., Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes. Inorganic Chemistry <\/em>2016,<\/strong> 55<\/em> (23), 12238-12253.<\/li>\n<\/ol>\n

     <\/p>\n","protected":false},"excerpt":{"rendered":"

    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 […]<\/p>\n","protected":false},"author":33170,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[],"tags":[],"class_list":["post-653","post","type-post","status-publish","format-standard","hentry"],"_links":{"self":[{"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/posts\/653","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/users\/33170"}],"replies":[{"embeddable":true,"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/comments?post=653"}],"version-history":[{"count":0,"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/posts\/653\/revisions"}],"wp:attachment":[{"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/media?parent=653"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/categories?post=653"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/blogs.otago.ac.nz\/keithgordon\/wp-json\/wp\/v2\/tags?post=653"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}