Title: Luminescent organometallic complexes with self-assembling properties Acronym: LUMINASSIL Contract: Project code: Proiect Experimental Demonstrativ 130PED/2017 (2017 – 2018) PN-III-P2-2.1-PED-2016-1536 Grant starting date: 03/01/2017 Grant duration: 1.5 years (03.01.2017 – 30.06.2018) Coordinator: CP III dr. Mihaela Iuliana AVĂDĂNEI Petru Poni Institute of Macromolecular Chemistry Contact: Mihaela Iuliana AVĂDĂNEI, e-mail: mavadanei@icmpp.ro

Project goals The project goal is to validate a demonstration technology for obtaining luminescent organometallic complexes with a well defined architecture, created by supramolecular non-covalent interactions, using silicon-containing Schiff bases ligands and different metal ions. The proposed project aims to create a new class of luminescent metal complexes based on Schiff bases containing flexible siloxane and silane units. The experimental model consists in the conceptual design, realization, full characterization by spectral methods and Single- Crystal X-Ray Diffraction and investigation of the photoluminescent potential of three mononuclear Zn(II) and Cu(II) metal complexes based on Schiff base ligands containing tetradimethyl-siloxane spacer and two complexes based on Schiff base ligands containing trimethylsilyl units, with self-assembling properties. The validated technology will be applied in fabrication of new luminescent supramolecular self-assemblies of homo/heteronuclear (3d, 3d/4f and 4f) metal complexes based on siloxane/silane- containing Schiff bases ligands.

Significance and innovation The oportunity, necessity and significance of the proposed project stem in development of a less explored scientific domain, with a real applicative potential in obtaining advanced hybrid materials. The project objectives combine the inorganic, organic and coordinative chemistry with photophysics and photochemistry for designing new supramolecular architectures with photosensitive properties. The innovative concept is the special design of the Schiff base ligand, the choice of the metal center, the special conditions for crystallization in order to obtain metal complexes in form of single crystals, with the ultimate aim to tune the emission color and intensity. The Schiff base ligands with siloxane or silyl units are less encountered in coordination chemistry and even less in the design of photoluminescent hybrid materials with supramolecular architecture, due to their high hydrophobicity and difficulty in obtaining single crystals.

Research Strategy The research strategy is based on the following scheme: design – synthesis – the analysis of the relationship between structure and properties – testing – verification – validation .

Preliminary results Organometallic complexes [Cu(LA)2], [Zn(LA)2] and [Zn(LB)2(H2O)2]2ClO4 M.-F. Zaltariov, M. Cazacu, M. Avadanei, S. Shova, M. Balan, N. Vornicu, A. Vlad, A. Dobrov, C.-D. Varganici, Synthesis, characterization and antimicrobial activity of new Cu(II) and Zn(II) complexes with Schiff bases derived from trimethylsilyl-propylp-aminobenzoate, Polyhedron 100 121–131 (2015) Mononuclear complexes ZnL1 and CuL2, where the ligands H2L1si H2L2 contain tetradimehylilsiloxane units A. Vlad, M.-F. Zaltariov, S. Shova, M. Cazacu, M. Avadanei, A. Soroceanu, P. Samoila, New Zn(II) and Cu(II) complexes with in situ generated N2O2 siloxane Schiff base ligands, Polyhedron 115 76–85 (2016)

Team Dr. Avadanei Mihaela Iuliana,CS III project director Dr. Shova Sergiu, CS II senior researcher Dr. Fifere Nicusor, CS post-doctoral researcher Dr. Zaltariov Mirela – Fernanda, CS post-doctoral researcher Ing. Vlad Angelica technician Ursu Doru technician