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

Abstract The field of supramolecular chemistry uses the molecular recognition for creation of extended architectures, where the building units are connected through hydrogen bonding, - stacking, CH-, cation-, lone pair- or anion - interactions. Molecular electronics, spintronics, optoelectronic devices or non-linear optics require special materials that combine several properties, such as magnetic, photoluminescence, electrochemical, chirality and conductivity. The design of organic – inorganic hybrid materials combines the properties of the ligand and those induced by the presence of metal (e.g. magnetism or luminescence) in such a way that the supramolecular structure must display specific properties resulting from the self-organization by weak intermolecular interactions. When using Schiff base ligands, coordination with the transition metal ions exploits their capacity to adopt four-, five- or six coordination modes, from where several supramolecular structures may result. The metal core plays a critical role in the photoluminescence of the complex. The colour of the emitted light is important, and changing the structure of the ligand from rigid to very flexible would affect the photophysical properties of the resulted complex. The dimensionality of a regular network (1D, 2D or 3D) is dependent on the geometrical features of the complex and on the type of intermolecular interactions. Using the concepts of supramolecular synthesis, crystal engineering and reversible intermolecular interactions, the molecular networks in crystalline state are obtained by using Schiff base ligands with tetradimethylsiloxane or trimethylsilyl units as flexibile and non-polar segments.

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.

Stage 1 - 2017: Experimental model for the synthesis of metal complexes of Schiff base ligands with flexible siloxane and silyl units Specific aims: Experimental model for the synthesis of metal complexes of Schiff base ligands with flexible siloxane and silyl units Study of the solution properties of the ligands and metal complexes: structural and photophysical studies. Photophysical properties in solid state. Validation of the experimental model in a lab instalation for obtaining homo- and heteronuclear complexes of Schiff bases synthesised according to the Specific Aim 1.1, with 3d and 3d/4f metal ions, having target properties and self-assembling abilities Dissemination of scientific results

Stage 2 - 2018: Validation of the experimental model in a lab installation Specific aims: Obtaining homo- and heteronuclear complexes of Schiff base ligands, synthesized with 4f metal ions, according to Activity 1.1, possessing target properties and self-assembling abilities Photophysical properties of 3d, 3d/4f si 4f metal complexes, in solution and solid state Dissemination of scientific results

Scientific results - flowchart Placement of LUMINASSIL scientific results on the scale of Technology Readiness Levels (TRL)

Scientific results – lab work Schiff base ligands with silane/siloxane units and 3d, 3d/4f and 4f metal complexes ten original ligands four 3d homonuclear complexes (two complexes with Cu2+, one complex with Mn2+ and one complex with Ni2+), six 3d/4f heteronuclear metal complexes (with Cu2+/La3+ and Cu2+/Dy3+), using three original ligands ten 4f metal complexes with La3+ and Dy3+ metal ions, using 5 original ligands based on 8-hydroxyquinoline-2-carboxyaldehyde five 4f metal complexes, using an original macrocylic ligand based on 2,6-diformyl-4-methylphenol two La3+ metal complexes using the original amine precursors 1,1,3,3-tetramethyldisiloxane-1,3-dyil)-bis-(methylene)-bis-(p-aminobenzoate) si dimethylsilane-bis-(methylene)-bis-(p-aminobenzoate) two metal complexes using ligands based on carboxylic acids and 4f metal ions (Eu3+ and Dy3+)

Scientific results – Papers “Unexpected co-crystallization of three species of Cu(II) complexes with different coordination geometry”, Mirela-Fernanda Zaltariov, Sergiu Shova, Rev. Roum. Chim. 62(4-5), 419-424 (2017) “Synthesis, structural characterization and properties of some novel siloxane-based bis-Schiff base copper(II), nickel(II) and manganese(II) Complexes”, Angelica Vlad, Mihaela Avadanei, Sergiu Shova, Maria Cazacu, Mirela-Fernanda Zaltariov, Polyhedron, 146, 129–135 (2018) “Photografted polymeric networks based on N-isopropylacrylamide: depth profiling by infrared spectroscopy”, Mihaela Avadanei, J. Appl. Polym. Sci., 135, 46048 (2018) “Effect of trimethylsilyl tails on the properties of (E)-2-hydroxy-3-((4- (((trimethylsilyl)methoxy)carbonyl)phenylimino)methyl)benzoic acid and (E)-2-hydroxy-3-((4- (((trimethylsilyl)methoxy)carbonyl)phenylimino)propyl)benzoic acid“, Mirela-Fernanda Zaltariov, Mihaela Avadanei, Mihaela Balan, Dragos Peptanariu, Nicoleta Vornicu, Sergiu Shova, under review Journal of Molecular Structure, manuscript ID: MOLSTRUC-D-18-01200, revision request. “Metallo-supramolecular assemblies of dinuclear Zn(II) and Mn(II) secondary building units (SBUs) and a bent silicon dicarboxylate ligand“, Georgiana-Oana Turcan-Trofin, Mihaela Avadanei, Sergiu Shova, Angelica Vlad, Maria Cazacu, Mirela-Fernanda Zaltariov, under review at Inorganica Chimica Acta, manuscript ID: ICA_2018_249, revision request. “Photochromic Cycle of Two N-Salicylidene-p-x-Anilines Revealed by the Dynamics over 10 Orders of Magnitude”, Mihaela Avadanei, João Pina, Carlos Serpa, Radu Tigoianu, Vasile Cozan, under review at Journal of Physical Chemistry, A. Manuscris ID: jp-2018-05047d.

Scientific results – Conferences Oral presentations Hybrid organic-inorganic materials based on lanthanide complexes of Schiff bases with siloxane units, with applications as photoluminescent devices, Mihaela Avadanei, Ionut Radu Tigoianu, Mirela-Fernanda Zaltariov, ModTech2018 International Conference, Modern Technologies in Industrial Engineering Constanta, Romania, 13-16.06.2018 Discrete structures built by flexible Schiff bases and Cu(II), Mn(II) and Ni(II) ions, Angelica Vlad, Mirela-Fernanda Zaltariov, Maria Cazacu, Mihaela Avadanei, RICCCE20 2017, Brasov, 06.09.2017-09.09.2017 Coordination polymers of Mn2+ and Zn2+ ions built with a bent silicon dicarboxylate ligand: synthesis, structural characterization and luminescence properties, Angelica Vlad, Mirela Zaltariov, Mihaela Avadanei, Sergiu Shova, Maria Cazacu, 9th International Conference in Chemistry Kyiv-Toulouse ICKT-9 (ICTK-9), 4-9.06. 2017, Kiev, Ucraina Iminodiacetate-thiosemicarbazone derivatives with high antiproliferative activity, Mirela Zaltariov, Sergiu Shova, 9th International Conference in Chemistry Kyiv-Toulouse ICKT-9 (ICTK- 9), 4-9.06. 2017, Kiev, Ucraina New hybrid materials based on thiosemicarbazone with high antiproliferative activity, Mirela Zaltariov, Congresul International al Universitatii "Apollonia“ din Iasi “Pregatim Viitorul Promovand Excelenta”, Editia a XXVII-a, 2-5.03 2017, Iasi, Romania

Scientific results – Conferences Posters One dimensional coodination polymer built by hexamanganese(III) clusters and a flexible dicarboxylate linker: structural characterization and self-assembly ability, Mirela-Fernanda Zaltariov, Maria Cazacu, Sergiu Shova, Mihaela Avadanei, RICCCE20 2017, Brasov, 06-09.09.2017 Thermal behavior of photo-aging PDMS polymeric films with embedded Lanthanum complexes based on polytopic ligands, Mirela-Fernanda Zaltariov, Cristian Dragos Varganici, Iuliana Spiridon, CEEC-TAC4,Chişinău, Republic of Moldova, 28-31.08.2017 Synthesis, structural characterization, photophysical properties and cytotoxic activity of Cu(II), Ni(II) and Mn(II) complexes based on new siloxane-containing Schiff base ligand, Angelica Vlad, Mihaela Avadanei, Dragos Peptanariu, Mirela-Fernanda Zaltariov, Maria Cazacu, Sergiu Shova, ZAI 2017, 5-6.10.2017, Iasi, Romania Lanthanide-based MOFs built on silicon-containing carboxylate ligands: synthetic strategies and properties evaluation, Mirela-Fernanda Zaltariov, Mihaela Avadanei, Georgiana-Oana Turcan-Trofin, Angelica Vlad, Maria Cazacu, Sergiu Shova, The 21st International Conference on Solid Compounds of Transition Elements, Vienna, Austria 25-29.03.2018 Synthesis, molecular characterization and biological activity of novel Schiff bases containing trimethylsilyl tails, Mirela-Fernanda Zaltariov, Dragos Peptanariu, Nicoleta Vornicu, Mihaela Avadanei, Mirela Zaltariov, Congresul International al Universitatii "Apollonia“ din Iasi “Pregatim Viitorul Promovand Excelenta”, Editia a XXVIII-a, Iasi, Romania, 1-4.03.2018

Scientific results – Book chapter, patents “Self-assembly in solution of metal complexes based on organo- siloxane ligands”, Mirela-Fernanda Zaltariov, Maria Cazacu, Carmen Racles, in Smart Materials. Integrated Design, Engineering Approaches, and Potential Application. Ed. Anca Filimon, Apple Academic Press, CRC Press, a Taylor and Francis Group, ISBN ebook: 978-1-315-16796-3. Patents “Procedeu de obtinere a retelelor metal – organice pe baza de acizi policarboxilici cu siliciu”, autori: Mirela – Fernanda Zaltariov, Angelica Vlad, Maria Cazacu „3-Trimetilsilil-1-propil-4-[(E)-1-(2-hidroxi-5metilbenzil)metilideneamino]- benzoat cu proprietati de senzor fluorescent"), authors: Mihaela Avadanei, Mirela – Fernanda Zaltariov

LUMINASSIL – project 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