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Abstracts of the talks presented at the Ladies' Day of FOR 2824 on May 20th, 2021

Prof. Dr. Anke Krueger Institut für Organische Chemie Julius-Maximilians-Universität Würzburg
Nanoscale Diamond, a Material for Many Applications Nanodiamond is a carbon allotrope with unique properties. It combines the unusual characteristics of diamond such as mechanical and chemical stability, biocompatibility and negative electron affinity with the properties of a nanoscale materials such as specific chemical reactivity. This lecture will introduce the synthesis, properties, functionalization and characterization of functional nanodiamond materials and will give examples for applications in biomedicine, imaging and catalysis.
Dr. Anita Zeidler Physics Department University of Bath, UK
Order within Disorder Amorphous materials are characterised by their inherent disorder. Atoms in the materials (e.g. liquids or glasses) are seemingly randomly distributed throughout. However, there is ordering in amorphous materials at a local and intermediate range. This interplay between the apparent disorder and order at near distances, however, gives rise to some of the most astonishing properties in glasses and liquids. Water, for example can under the right conditions (potentially attained in space on distant planets) form glasses with vastly different structures and hence properties. Closer to home, glasses are not restricted to stoichiometric compositions, giving the scientist an infinite number of possibilities to tweak the material properties. Applying high pressures and/or temperatures will push these glasses even further away from equilibrium. The sky is the limit.
Prof. Dr. Barbara Kirchner Mulliken Center for Theoretical Chemistry University of Bonn
Chirality and Proton activity from molecular to ionic liquids
	Ionic liquids (ILs) [1] are playing a role in many exciting applications as and for materials.[2] They are used in so different areas as in electrochemistry, catalysis, in coal processing, in pharmaceutical applications.[2] Understanding which one of all the possibilities is the right ionic liquid to use is the key to the successful outcome of the particular applications. Therefore, an understanding of the molecular level behavior,[3] of the given liquid itself is desirable if the full potential of the solvent should be reached. For example, the structure-directing or template effect [4,5,6] has been invoked several times for ILs to explain the different outcome in material synthesis when varying the IL. We will first discuss chirality and its detection,[9] which plays an important role for the understanding of pharmaceuticals in ILs or pharmaceutical ILs. [10] Second, we focus on electrolyte applications of ILs. In such systems, the association of the ions to form ion pairs or other, low charge aggregates is a long discussed issue,[7] since it can affect the manner and the extent of conduction through changing the number of mobile charged species in the solution. Structural diffusion in ILs [8] can be connected to electrochemical applications. In particular, the proton transfer ability of solvents is a highly important feature for electrolytes and for solvents in synthesis as well.
References [1] P. Wasserscheid, P. and Welton T., eds. Ionic liquids in synthesis. John Wiley & Sons, 2008. [2] Balducci, A. "Ionic liquids in lithium-ion batteries." Springer, Cham, 2017. 1-27; Lynden-Bell, R. M. et al,. PCCP 14.8 (2012): 2693; Welton, T. Coord. Chem. Rev. 248.21-24 (2004): 2459; Bica, K., et al. Chem. Comm. 48.41 (2012): 5013; F. Cui et al. Fuel 217 (2018) 508; Hough, W. L. et al. Bull. Chem. Soc. Jap. 80.12 (2007): 2262; F., R. Branco, et al. (2011), ChemMedChem, 6: 975 [3] Kirchner, B., et al. WIREs 5.2 (2015): 202. Schröder, C., J. Chem. Phys. 135.2 (2011): 024502; Pádua, AAH, et. al Acc. Chem. Res. 40.11 (2007): 1087; E. Izgorodina, Chem. Rev. 117(10), 2017; V. Ivaništšev et al. J. Phys. Chem. C, 2014, 118, 11, 5841; Zahn, S. and Cybik, R.; Am. J. Nano Res. App. 2014, 2, 19 [4] Cooper, E. R., et al. Nature 430.7003 (2004): 1012; Santner, S.; Heine, J.; Dehnen, Angew. Chem. Int. Ed. 2016, 55, 876–893. [5] Elfgen, R. et al. Acc. Chem. Res. 50.12 (2017): 2949 [6] Canongia Lopes, JNA and Pádua AAH; J. Phys. Chem. B 110.7 (2006): 3330. [7] T. Cremer, et al., Chem. Eur. J., (2010), 16, 9018; N. Taccardi, et al., Chem. Eur. J. 2012, 18, 8288; B. Kirchner et al., J. Phys.: Condens. Matter, (2015), 27, 463002; O. Hollóczki, et al., PCCP. (2014), 16, 16880 [8] Del Pópolo, M. G. et al. J. Phys. Chem. B 110.17 (2006): 8798; B. Kirchner and A. P. Seitsonen, Inorg. Chem., (2007), 46, 2751; R. Elfgen, et al., Z. Anorg. Allg. Chem. (2017) 643, 41; J. Ingenmey et al. JCP (2018), 148:19; J. Ingenmey et al., ChemSusChem (2018), 11, 1900; D. S. Firaha et al. , J. Chem. Phys. (2016) 145, 204502, O Hollóczki, et al. Chem-Eur. J. 24 (61), 16193; J. Ingenmey, M. von Domaros, E. Perlt, S. P. Verevkin, B. Kirchner, J. Chem. Phys. (2018), 148, 193822 [9] M. Thomas and B. Kirchner J. Phys. Chem. Lett. (2016), 7, 509; Kirchner et al. Adv. Theory Simul. (2021), 4, 2000223, J. Phys. Chem. B (2020), 124, 7272 [10] Vasiloiu, M., et al Cat. today 200 (2013): 80
Prof. Dr. Katja Heinze Department of Chemistry Johannes Gutenberg University Mainz
Spin-Flip Emission with Earth-Abundant Metal Ions The development of metal complexes with Earth-abundant first row transition metal ions as emitters for (PH)OLEDs, as dyes for DSSCs and sensor devices or as photocatalysts is very challenging, due to the typically fast non-radiative deactivation of the electronically excited states.[1] Beyond the classically exploited luminescent charge transfer states, metal-centered states with small excited state distortion can become emissive. This is realized in so-called spin-flip emitters.[1,2] I will devise a deeper understanding of the fundamentals for high luminescence quantum yields and lifetimes (Figure 1, left) followed by emerging applications of chromium(III) complexes, especially molecular ruby and its derivatives (Figure 1, right) in sensing, catalysis, upconversion, and circularly polarized luminescence.[2-9] Developments toward luminescent spin-flip emitters with Earth-abundant metal ions beyond chromium will be reported.[10]
	Figure 1. Jablonski diagram with relevant photophysical processes of octahedral d3-metal complexes and “molecular rubies” [Cr(ddpd)₂]3+ [3] and [Cr(tpe)₂]3+ [8]. Detailed view
[1] C. Förster, K. Heinze, Chem. Soc. Rev. 2020, 49, 1057. [2] S. Otto, M. Dorn, C. Förster, M. Bauer, M. Seitz, K. Heinze, Coord. Chem. Rev. 2018, 359, 102. [3] S. Otto, M. Grabolle, C. Förster, C. Kreitner, U. Resch-Genger, K. Heinze, Angew. Chem. Int. Ed. 2015, 54, 11572. [4] S. Otto, A. M. Nauth, E. Ermilov, N. Scholz, A. Friedrich, U. Resch-Genger, S. Lochbrunner, T. Opatz, K. Heinze, ChemPhotoChem 2017, 1, 344. [5] S. Otto, J. Harris, K. Heinze, C. Reber, Angew. Chem. Int. Ed. 2018, 57, 11069. [6] C. Wang, S. Otto, M. Dorn, E. Kreidt, J. Lebon, L. Sršan, P. Di Martino-Fumo, M. Gerhards, U. Resch-Genger, M. Seitz, K. Heinze, Angew. Chem. Int. Ed. 2018, 57, 1112. [7] C. Dee, F. Zinna, W. R. Kitzmann, G. Pescitelli, K. Heinze, L. Di Bari, M. Seitz, Chem. Commun. 2019, 55, 13078. [8] S. Treiling, C. Wang, C. Förster, F. Reichenauer, J. Kalmbach, P. Boden, J. P. Harris, L. M. Carrella, E. Rentschler, U. Resch-Genger, C. Reber, M. Seitz, M. Gerhards, K. Heinze, Angew. Chem. Int. Ed. 2019, 58, 18075. [9] J. Kalmbach, C. Wang, Y. You, C. Förster, H. Schubert, K. Heinze, U. Resch-Genger, M. Seitz, Angew. Chem. Int. Ed.* 2020, 59, 1884-18808. [10] M. Dorn, J. Kalmbach, P. Boden, A. Päpcke, S. Gómez, C. Förster, F. Kuczelinis, L. M. Carrella, L. Büldt, N. Bings, E. Rentschler, S. Lochbrunner, L. González, M. Gerhards, M. Seitz, K. Heinze, J. Am. Chem. Soc. 2020, 142, 7947.
Prof. Dr. Stefanie Gräfe Institute of Physical Chemistry and Institute of Applied Physics Abbe Center for Photonics Friedrich Schiller University Jena
Plasmonic hybrid systems in external light fields: can we achieve sub-nanometer lateral resolution using near-field techniques? What is the ultimate spatial resolution that can be achieved with near-field methods? In current experiments, for example based on tip-amplified Raman scattering (TERS), there is increasing evidence for an extremely high spatial resolution on the nanometer or even sub-nanometer scale. In this talk, I will present some of these experiments of our collaboration partner, Prof. Volker Deckert from Jena, as well as the first results of our calculations. For the theoretical description of such plasmonic hybrid systems in external light fields, it is necessary to describe both the electromagnetic interaction and the more chemical effects equally. Our calculations show pronounced changes of the Raman spectrum under non-resonant and resonant conditions and support the possibility of sub-nanometer spatial resolution.

References: [1] K. Fiederling, M. Abasifard, M. Richter, V. Deckert, S. Gräfe, S. Kupfer, “A Full Quantum Mechanical Approach Assessing the Chemical and Electromagnetic Effect in TERS”, Nanoscale, 2020, 12, 6346-6359. [2] F. Latorre, S. Kupfer, T. Bocklitz, D. Kinzel, S. Trautmann, S. Gräfe, V. Deckert, „Spatial resolution of tip-enhanced Raman spectroscopy – DFT assessment of the chemical effect”, Nanoscale 2016, 8, 10229 – 10239.

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