Università degli Studi di Cagliari DOTTORATO DI RICERCA Scienze e Tecnologie Chimiche XXXI Ciclo Anilate-based Molecular Building Blocks for Metal-Organic Frameworks and Molecular Conductors Settore scientifico disciplinare CHIM/03 Presentata da: Suchithra Ashoka Sahadevan Coordinatore Dottorato: Prof. Stefano Enzo Tutor: Prof. Maria Laura Mercuri Dr. Narcis Avarvari Esame finale anno accademico 2018/19 THESE DE DOCTORAT DE L'UNIVERSITE D'ANGERS COMUE UNIVERSITE BRETAGNE LOIRE ECOLE DOCTORALE N° 596 Matière Molécules et Matériaux Spécialité: Chimie des matériaux Par ASHOKA SAHADEVAN SUCHITHRA Anilate-based Molecular Building Blocks for Metal- Organic Frameworks and Molecular Conductors Thèse présentée et soutenue à Cagliari, le 6 février 2019 Unité de recherche: Laboratoire MOLTECH-Anjou, Université d’Angers Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari Thèse N° : 161340 Rapporteurs avant soutenance: Composition du Jury: Marius ANDRUH, Professeur, Université de Bucarest Miguel Julve OLCINA, Professeur, Universitat de (Romania) Président València (Spain) Olivier MAURY, Directeur de Recherche CNRS, Manuel ALMEIDA, Professeur, Universitat de lisbon Université de Lyon (France) (Portugal) Adolfo SPEGHINI, Professeur, Université de Verona (France) Maria laura MERCURI, Professeur, Université de Cagliari (Italy) Narcis AVARVARI, Directeur de Recherche CNRS, Université de Angers (France) III This work has been performed in the framework of a Co-joint PhD thesis between the Dipartimento di Scienze Chimiche e Geologiche, University of Cagliari (Italy) and Moltech Anjou Laboratory, University of Angers (France). V Dedicated to my family… VII Acknowledgments Firstly, I would like to express my sincere gratitude to my supervisors, Prof. Maria Laura Mercuri and Dr. Narcis Avarvari, for their continuous support during my Ph.D.; for their patience, motivation and invaluable advices both in research as well as in career. I wish to thank all the members of the research group (Cagliari University), Prof. Enzo Cadoni, my friends and the coworkers Mariangela Oggianu and Noemi Monni for the assistance and encouragement they provided at all levels of the research project. Special thanks to Noemi for all the endless discussions we had in professional and personal life and for being a great friend. I also thank my colleagues and friends Marco, Joanna and Rosita with whom I shared the office and for all the memorable moments we had. I also wish to thank all my Ph.D. colleagues with whom I could share all the stress and anxiety. Thanks Swapneel for all the fun-filled conversations which we had during the tea breaks. Thanks for being a great friend. I would also like to acknowledge all the members from Moltech-Anjou Laboratory (Angers University), Alexandre Abhervé deserves special thanks for the support and the time we spent in fruitful discussions on several aspects of the work. Dr. Cécile Mézière, Dr. Flavia Pop, Dr. Magali Allain and Prof. Nicolas Mercier are also kindly acknowledged for all the assistance and discussions. I also thank all my groupmates and colleagues Cristina, Maurizio, Kevin, Oleg, Nataliya, Nabil and Marwa for all the fun we had during my stay at Angers. I am already missing our Coffee break discussions and barbeque time. My sincere thanks to Prof. Masahiro Yamashita, who provided me an opportunity to spent a short-term research stay in his lab (Yamashita Lab, Tohoku University), and giving me all access to the laboratory and research facilities. I would also like to acknowledge Dr. Goulven Cosquer, who helped me with the magnetic measurements, Rasel, for the X-Ray measurements and throughout my stay there. I also thank all the other people from the lab especially Dr. Soumava Biswas, Dr. Leena Mandal, and Afrin. I would also like to extend my sincere gratitude to all our collaborators. Prof. Francesco Quochi and Prof. Giovanni Bongiovanni (Dipartimento di Fisica, Cagliari University) are greatly acknowledged for luminescent measurements and for all the discussions. Dr. Daniela Marongiu is also sincerely acknowledged for the AFM measurements. Prof. Carla Cannas (Dipartimento di Chimica, Cagliari University) is kindly acknowledged for the HR-TEM measurements and for the contribution to the discussions. Prof. José Ramòn Galàn (Tarragona University) and Dr. Cristina Sàenz de Pipaon, are kindly acknowledged for magnetic measurements and their contributions to the discussion. IX Dr. Pascale Auban-Senzier (Paris-Sud University) and Prof. Hengbo Cui (Condensed Molecular Materials Laboratory, Riken) are gratefully acknowledged for conductivity measurements and Prof. Enric Canadell (Barcelona University) is acknowledged for Band Structure calculations. Dr. Bruno J. C. Vieira and Prof. João C. Waerenborgh (Universidade de Lisboa) are acknowledged for Mössbauer measurements Prof. Pere Alemany (Universitat de Barcelona) is kindly acknowledged for theoretical calculations. Dr. Valerie Bonin (Angers University) is acknowledged for elemental analyses, Dr. Ingrid Freuze (Angers University) are acknowledged for MS analyses and Dr. Sylvie Dabos-Seignon (University of Angers) are acknowledged for AFM characterization. This work would not have been possible without the financial support from the ItalianMinistero dell‘Istruzione e della Ricerca (MIUR), which has financed my PhD grant, and the Regione Autonoma della Sardegna, Cagliari and Angers Universities, INSTM, CNRS and Fondazione Banco di Sardegna. I wish to thank all my Indian friends in Cagliari Ranjth, Swapneel, Barnali, Amitash, Rahul, Hema, and Ashish for making a home away from home. Last but not the least, I would like to thank my family: my parents for encouraging and inspiring me to follow my dreams and to my sisters Smitha and Soorya with whom I grew together sharing and supporting all the moments and and special thanks to Kiran for supporting me along the way. ABSTRACT This work reports on the design, synthesis and characterization of novel anilate-based functional molecular materials showing luminescent, magnetic and/or conducting properties. The family of anilate ligands comprises several derivatives obtained by introducing various substituents (H, F, Cl, Br, I, CN, etc.) at the 3 and 6 positions of the common 2,5-dihydroxy-1,4-benzoquinone framework. Their electronic/structural features, coordination modes, ability to mediate magnetic exchange interactions between coordinated d and/or f-metal centers, and to work as efficient antenna ligands towards NIR lanthanide ions, make them suitable candidates for the preparation of the materials reported. In Chapter 1, the synthesis of a multifunctional mixed-valence FeIIFeIII anilate-based coordination polymer, obtained by using the chlorocyanilate ligand (ClCNAn2-), formulated as II III [TAG][Fe Fe (ClCNAn)3]·(solvate) (TAG = tris(amino)-guanidinium) is reported. This compound is characterized by single crystal X-Ray, at 150K and 10K, magnetic, m ss uer and conductivity measurements. Moreover, correlation of conductivity difference between anilate and pioneer oxalate based FeIIFeIII 2D coordination polymers are explained using theoretical calculations (small-polaron hopping model). In Chapter 2, the series of 2D layered coordination polymers based on chlorocyanilate ligand as III building blocks formulated as [Ln2(ClCNAn)3(DMF)6]·(DCM)x (Ln = Yb (1) (x = 0), Nd (2) and Er (3) (x = 2)) are reported. The synthesis, structural characterization, photophysical studies, time-resolved photoluminescence studies performed on both the bulk and nanosheets, effects induced by the exfoliation process on the photo-physical properties of the nanosheets are discussed. In Chapter 3, the new family of NIR-emitting lanthanide coordination polymers based on chlorocyanilate ligand and carboxylate ligands (di-hydroxy-terephthalic acid (DOBDC) and tetrafluoroterephthalic acid (F4-BDC)), which are the commonly used ligands to obtain 2D layered materials are reported. These systems are formulated as III [Ln4(ClCNAn)5(DOBDC)1(DMSO)10]·(DMSO)2 (Ln - Yb (1), Er (2)) [Ln2(ClCNAn)2(F4- III BDC)(DMSO)6] (Ln – Yb (3), Er (4)). Structural characterizations along with time-resolved photoluminescence studies on these compounds are described. XI In Chapter 4, series of 2D layered coordination polymers based on chlorocyanilate ligand and III Dy are reported. These compounds are formulated as [Dy2(ClCNAn)3(DMSO)6] (1), [Dy2(ClCNAn)6(DMSO)6] (1'), [Dy2(ClCNAn)3(DMF)6](CH2Cl2) (3), (Me2NH2)2[Dy2(ClCNAn)4(H2O)2]·(DMF) (4). The synthesis, structural characterization along with its magnetic characterization is described. In Chapter 5, using the above-mentioned anilate ligands with the BEDT-TTF organic donor, purely organic semiconductors formulated as [BEDT-TTF]2[HClCNAn] (1) and [BEDT- TTF][HCl2An] (2) are obtained by electrocrystallization. Their structural characterization, transport properties and band structure calculation are reported. In Chapter 6, structural diversity and physical properties of П-d hybrid multifunctional 3- paramagnetic molecular conductors obtained by combining BEDT-TTF and [Fe(ClCNAn)3] as conducting and magnetic carrier respectively are reported. These compounds are formulated as [BEDT-TTF]4[Fe(ClCNAn)3]·3H2O (1) and [BEDT-TTF]5[Fe(ClCNAn)3]2·2CH3CN (2). Their structural characterization, transport properties and magnetic properties are described. The framework of the thesis is as follows: Part I - General Introduction on Molecular Materials, State of the Art on Anilate-based MOFs and Coordination Polymers and Molecular Conductors