Surface-based self-assembly of 3-D spintronic coordination nano-architectures

Consortium:
	Prof. Dr. Johannes V. Barth, Munich Technical University of Munich Surface and Interface Physics
	Dr. Svetlana Klyatskaya, Karlsruhe Karlsruhe Institute of Technology Molecular Materials
	Dr. Anthoula C. Papageorgiou, Munich Technical University of Munich Surface and Interface Physics
	Prof. Dr. Mario Ruben, Karlsruhe Karlsruhe Institute of Technology Molecular Materials
Project:	Surface-Based Self-Assembly 3-D Spintronic Coordination Nano-Architectures

Abstract:	Within the frame of COORNETs we aim at the construction of robust 3-D spintronic coordination networks at well-defined interfaces under ultra-high vacuum conditions using sublimation and/or electrospray ionization (ESI) deposition of building blocks. The 3-D self-assembly process exploits metal-ligand interactions between custom-designed molecular linkers and magnetically active metal centers to afford functional nano-architectures. We notably plan to engineer templated coordination networks providing different magnetic features, incorporating (i) Fe(II) based spin-crossover (SCO) or (ii) tetrapyrrole molecules functionalized with magnetic transition metals or lanthanides. Moreover, enhancement of electric conductivity will be explored by (i) inclusion of photopolymerizable moieties in the MOF building block or (ii) engineering of the coordination node. The physicochemical properties and functional behaviour of the obtained surface-based 3-D networks will be studied by molecular-level scanning tunneling microscopy/spectroscopy observations (STM/STS), complemented by high-resolution X-ray spectroscopies, X-ray magnetic circular dichroism (XMCD), and a set of complementary sophisticated methods. Input: Our collaboration relies on a longstanding expertise in the self-assembly and the characterization of molecule-based coordination and covalent networks or nanostructures on surfaces (with more than 35 joint publications during the last decade). In particular, we are herein interested in spintronic materials and devices, including their structural, electronic, magnetic or mechanical properties. The relevant proficiency relies on the conception of carefully tailored and de-novo synthesized molecular bricks, as well on the development of assembly protocols to steer processes and spatial organization under near-surface conditions. The structural, electrical and magnetic characterization of the obtained surface-based networks and nano- architectures is achieved mainly by a combination of STM/STS and X- ray spectroscopy techniques. Output offered: We plan to obtain new classes of spintronic coordination networks with unique functional properties, in particular (i) switchable magnetic properties based on spin crossover compounds and porphyrins/phthalocyanines combined with (ii) spintronic conductivity through engineering of either the coordination node or the functionalizing of linker species for post- synthetic photopolymerization.

Publications:
	R. Zhang, J. Liu, Y. Gao, M. Hua, B. Xia, P. Knecht, A. C. Papageorgiou, J. Reichert, J. V. Barth, L. Huang, H. Xu, and N. Lin „On-surface synthesis of a semiconducting 2D metal-organic framework Cu3(C6O6) exhibiting dispersive electronic bands„ Angew. Chem. Int. Edit. 2020, 59, 2669-2673 DOI: 10.1002/anie.201913698
	J. I. Urgel, D. Écija, S. Vijayaraghavan, M. Pörtner, M.-L. Bocquet, W. Auwärter, and J. V. Barth „In-situ growth of gadolinium phthalocyaninato sandwich complexes on the Ag(111) surface„ ChemPhysChem 2019, 20, 2301-2304 DOI: 10.1002/cphc.201900253
	W. Wernsdorfer, M. Ruben „Synthetic engineering of the Hilbert space of molecular qudits: Isotopologue chemistry„ Adv. Mater. 2019, 31, 1806687 DOI: 10.1002/adma.201806687
	Z. Chen, T. Lin, L. Zhang, Dr. Lei Zhang, B. Xiang, H. Xu, F. Klappenberger, J. V. Barth, S. Klyatsakya, and M. Ruben „Surface-dependent chemoselectivity in C–C coupling reactions„ Angew. Chem., Int. Ed. 2019, 58, 8356-8361 DOI: 10.1002/anie.201900636
	F. Schleicher, M. Studniarek, K. S. Kumar, E. Urbain, K. Katcko, J. Chen, T. Frauhammer, M. Hervé, U. Halisdemir, L. M. Kandpal, D. Lacour, A. Riminucci, L. Joly, F. Scheurer, B. Gobaut, F. Choueikani, E. Otero, P. Ohresser, J. Arabski, G. Schmerber, W. Wulfhekel, E. Beaurepaire, W. Weber, S. Boukari, M. Ruben, M. Bowen „Linking electronic transport through a spin crossover thin film to the molecular spin state using X-ray absorption spectroscopy operando techniques„ ACS Appl. Mater. Interfaces 2018, 10, 31580-31585 DOI: 10.1021/acsami.8b11495
	J. Hellerstedt, C. Ales, M. Svec, B. de la Torre,M. Moro-Lagares,T. Chutora,B. Papoušková, G. Zoppellaro, P. Mutombo, M. Ruben, R. Zboril, and P. Jelinek „On-surface structural and electronic properties of spontaneously formed Tb2Pc3 single molecule magnets„ Nanoscale 2018, 10, 15553-15563 DOI: 10.1039/C8NR04215B
	D. Écija, J. I. Urgel, A. P. Seitsonen, W. Auwärter, J. V. Barth „Lanthanide-directed assembly of interfacial coordination architectures–from complex networks to functional nanosystems„ Acc. Chem. Res. 2018, 51, 365-375 DOI: 10.1021/acs.accounts.7b00379
	A. C. Papageorgiou, L. Jiang, S. C. Oh, B. Zhang, Ö. Sağlam, Y. Guo, J. Reichert, A. B. Marco, D. Cortizo-Lacalle, A. Mateo-Alonso, and J. V. Barth „Tuning the ease of formation of on-surface metal-adatom coordination polymers featuring diketones„ Nanoscale 2018, 10, 9561-9568 DOI: 10.1039/c8nr02537a
	S. K. Kuppusamy, B. Heinrich, J. Arabski, G. Schmerber, M. Bowen, S. Boukari, E. Beaurepaire, J. Dreiser, and M. Ruben „Engineering on-surface spin crossover: Spin-state switching in a self-assembled film of vacuum sublimable functional molecule„ Adv. Mater. 2018, 30, 1705416 DOI: 10.1002/adma.201705416
	P. Knecht, N. Suryadevara, B. Zhang, J. Reichert, M. Ruben, J. V. Barth, S. Klyatskaya, and A. C. Papageorgiou „The self-assembly and metal adatom coordination of a linear bis-tetrazole ligand on Ag(111)„ Chem. Commun. 2018, 54, 10072-10075 DOI: 10.1039/C8CC04323J
	L. Jiang, B. Zhang, G. Médard, A. P. Seitsonen, F. Haag, F. Allegretti, J. Reichert, B. Kuster, J. V. Barth, and A. C. Papageorgiou „N-Heterocyclic carbenes on the close packed coinage metal surfaces: Bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu„ Chem. Sci. 2017, 8, 8301-8308 DOI: 10.1039/C7SC03777E