Hybrid organic-inorganic magnetic and multifuntional systems

Low-dimensional Inorganic and Hybrid Organic-Inorganic magnetic systems

We develop different techniques for the quantitative analysis of magnetic interactions in low dimensional compounds ( 0D , 1D, 2D ) from the experimental magnetic measurements . We were particularly interested in hydroxynitrates series of transition metals that have proven to be very good model compounds to understand the effects of structure and spin dimensionality and of the anisotropy on the behavior of 1D or 2D magnetic systems with competing interactions. This type of analysis of the relationship between structure and property is extended to various coordination networks (from finite molecules to MOFs) synthesized in our team or interesting colleagues from other laboratories. Some literal expressions of the magnetic susceptibility for complex chains have been established and are used in the literature. Our approach is sometimes supplemented by DFT calculations of the electronic structure of the solid. We are currently interested in the magnetism of the f electrons ions.1

Figure 1. View of the structure of [Ni3(m3-OH)2((k1-k1)-(k1-k1)-m4 TDC)2(H2O)4]nalong a (Left) and thermal variation of the magnetic susceptibility. (The full line corresponds to the best fit) (Middle). Interaction scheme considered in the chain model used for the parameterization of the experimental curves (Right).

1.             (a) Rueff, J.-M.; Masciocchi, N.; Rabu, P.; Sironi, A.; Skoulios, A., Synthesis, Structure and Magnetism of Homologous Series of Polycrystalline Cobalt Alkane Mono- and Dicarboxylate Soaps. Chemistry – A European Journal 2002,8 (8), 1813; (b) Souletie, J.; Rabu, P.; Drillon, M., Scaling Theory Applied to Low Dimensional Magnetic Systems. In Magnetism: Molecules  to Materials Miller, J. S.; Drillon, M., Eds. Wiley VCH Verlag GmbH & Co. KGaA Weinheim: 2005; Vol. V, pp 347-377; (c) Beghidja, A.; Rogez, G.; Rabu, P.; Welter, R.; Drillon, M., magnetic-chiralo. J. Mater. Chem. 2006,16, 2715-2728; (d) Bauer, E. M.; Bellitto, C.; Righini, G.; Colapietro, M.; Portalone, G.; Drillon, M.; Rabu, P., Comparison of the Structure and Magnetic Order in a Series of Layered Ni(II) Organophosphonates, Ni[(RPO3)(H2O)] (R = C6H5, CH3, C18H37). Inorg. Chem. 2008,47 (23), 10945-10952; (e) Mantion, A.; Massuger, L.; Rabu, P.; Palivan, C.; McCusker, L. B.; Taubert, A., Metal-Peptide Frameworks (MPFs): « Bioinspired » Metal Organic Frameworks. J. Am. Chem. Soc. 2008,130 (8), 2517-2526; (f) Livage, C.; Guillou, N.; Rabu, P.; Pattison, P.; Marrot, J.; Ferey, G., Bulk homochirality of a 3-D inorganic framework: ligand control of inorganic network chirality. Chemical Communications 2009,  (30), 4551-4553; (g) Lhoste, J.; Perez-Campos, A.; Henry, N.; Loiseau, T.; Rabu, P.; Abraham, F., Chain-like and dinuclear coordination polymers in lanthanide (Nd, Eu) oxochloride complexes with 2,2[prime or minute]:6[prime or minute],2[prime or minute][prime or minute]-terpyridine: synthesis, XRD structure and magnetic properties. Dalton Trans. 2011,40 (36), 9136-9144; (h) Falaise, C.; Volkringer, C.; Vigier, J.-F.; Beaurain, A.; Roussel, P.; Rabu, P.; Loiseau, T., Isolation of the Large {Actinide}38 Poly-oxo Cluster with Uranium. J. Am. Chem. Soc. 2013,135 (42), 15678-15681.

Layered hydroxides : model magnetic hybrid compounds and variation   

Series of new hybrid materials with original magnetic properties have been prepared on the basis of simple layered hydroxides (LSH) M2(OH)3A (M = Co, Cu and A = NO3, OAc, …). At first we investigated the mechanisms of interactions and structural factors influencing the magnetic properties of hybrid based LSH. Then more and more complex anions were immobilized and grafted within the interlayer space to explore the possibility of the emergence of new features. These systems are good models for understanding the correlations between structure and physical properties provided by molecular entities grafted onto hydroxide sheets and coordinated to the metal ions.

Figure 2. Our approach for the synthesis of magnetic and bi-functional layered hybrid systems.

We especially highlighted structure –property- relationships and magnetic interaction mechanisms (exchange, dipolar, spin polarization) in layered hybrid systems, the influence of the inter-plane distance, the possibility to obtain flexible and adaptable magnetic layered structures.2

2.             (a) Laget, V.; Hornick, C.; Rabu, P.; Drillon, M.; Ziessel, R., Molecular magnets: Hybrid organic-inorganic layered compounds with very long-range ferromagnetism. Coord. Chem. Rev. 1998,178-180 (Part 2), 1533; (b) Huang, Z. L.; Drillon, M.; Masciocchi, N.; Sironi, A.; Zhao, J. T.; Rabu, P.; Panissod, P., Ab-initio XRPD crystal structure and giant hysteretic effect (H(c) = 5.9 T) of a new hybrid terephthalate-based cobalt(II) magnet. Chem. Mater. 2000,12 (9), 2805-2812; (c) Feyerherm, R.; Loose, A.; Rabu, P.; Drillon, M., Neutron diffraction studies of canted antiferromagnetic ordering in CoII hydroxide terephtalate. Solid State Sciences 2003,5 (2), 321-326; (d) Rabu, P.; Drillon, M., Layered Organic-Inorganic Materials: A Way towards Controllable Magnetism. Adv. Engin. Mater. 2003,5 (4), 189-210; (e) Demessence, A.; Rogez, G.; Rabu, P., Grafting of Thiophenecarboxylates into Magnetic Transition Metal Hydroxide Layers. Chem. Mater. 2006,18, 3005-3015; (f) Ruiz, E.; Llunell, M.; Cano, J.; Rabu, P.; Drillon, M.; Massobrio, C., Theoretical Determination of Multiple Exchange Couplings and Magnetic Susceptibility Data in Inorganic Solids: The Prototypical Case of Cu<sub>2</sub>(OH)<sub>3</sub>NO<sub>3</sub>. J. Phys. Chem. B 2006,110 (1), 115-118; (g) Mesbah, A.; Rabu, P.; Sibille, R.; Lebègue, S.; Mazet, T.; Malaman, B.; François, M., From Hydrated Ni3(OH)2(C8H4O4)2(H2O)4 to Anhydrous Ni2(OH)2(C8H4O4): Impact of Structural Transformations on Magnetic Properties. Inorg. Chem. 2014.

Toward the engineering of multifunctional complex architectures

The most recent work has focused on the development of anion exchange as synthetic route. This route is relatively versatile and we were able to obtain multifunctional compounds using magnetic organometallic or organic anions as building blocks. Such blocks were chosen to bring fluorescence, chirality or bio-related functionalities. The coupling between the properties is at the heart of our current concerns. Results deal with the coupling between magnetic and optical properties, including fluorescence or chirality . In the case of hydroxides functionalized with oligopeptides, we studied the effect of the presence of redox and fluorescent groups as well as the nature of the pendant chains on the overall properties of the final hybrid material. Some rules can be proposed in a way that the synergy occurs between magnetism and optical property (grafting method , luminescence efficiency , λabs / em , lifetime of the excited state ) . This approach to the bi- functional material is advantageous since photoactive molecules grafted in a crystalline structure provide a network of organized molecules that can create synergy. Either complex organic molecules or electronic coupler (conjugated systems) may play a structural role and the existence of an iono – covalent link between subcomponents promotes synergy between the properties from each entity. Similarly, we are interested in the structuration of functional solids by molecules with self-assembly properties. The aim is to study the effect of a rearrangement of the inter-layer space and the effect of confinement on the self-assembly system on the properties. We succeed also in the post-functionalization of hydroxides by in situ chemical reaction on pre-inserted precursors. Recent results, in other systems than hydroxides as well, show that our approach is appropriate for providing complex multifunctional materials.3

Figure 3. Exchange reactions of typical functional molecules in layered hydroxides.

3.             (a) Delahaye, É.; Diop, M.; Welter, R.; Boero, M.; Massobrio, C.; Rabu, P.; Rogez, G., From Salicylaldehyde to Chiral Salen Sulfonates – Syntheses, Structures and Properties of New Transition Metal Complexes Derived from Sulfonato Salen Ligands. European Journal of Inorganic Chemistry 2010,  (28), 4450 – 4461; (b) Demessence, A.; Yassar, A.; Rogez, G.; Miozzo, L.; De Brion, S.; Rabu, P., Synthesis, optical and magnetic properties of hybrid ,[prime or minute]-oligothiophenecarboxylates/transition metal hydroxide multilayered compounds. J. Mater. Chem. 2010,20 (42), 9401 – 9414; (c) Delahaye, E.; Xie, Z.; Schaefer, A.; Douce, L.; Rogez, G.; Rabu, P.; Gunter, C.; Gutmann, J. S.; Taubert, A., Intercalation synthesis of functional hybrid materials based on layered simple hydroxide hosts and ionic liquid guests – a pathway towards multifunctional ionogels without a silica matrix? Dalton Trans. 2011,40 (39), 9977-9988; (d) Rogez, G.; Massobrio, C.; Rabu, P.; Drillon, M., Layered hydroxide hybrid nanostructures: a route to multifunctionality. Chem. Soc. Rev. 2011,40 (2), 1031-1058; (e) Delahaye, E.; Eyele-Mezui, S.; Diop, M.; Leuvrey, C.; Foix, D.; Gonbeau, D.; Rabu, P.; Rogez, G., Functional Heterometallic Layered Hybrid Magnets by Double Ion-Exchange. European Journal of Inorganic Chemistry 2012,  (16), 2731-2740; (f) Si, S.; Taubert, A.; Mantion, A.; Rogez, G.; Rabu, P., Peptide-intercalated layered metal hydroxides: effect of peptide chain length and side chain functionality on structural, optical and magnetic properties. Chemical Science 2012,3 (6), 1945 -1957; (g) Palamarciuc, O.; Delahaye, E.; Rabu, P.; Rogez, G., Microwave-assisted post-synthesis modification of layered simple hydroxides. New Journal Of Chemistry 2014.

Figure 4. the OPV-tétracarboxylate molecule inserted between Ni(II) planes and thermal variation of the luminescence of the ligand in the hybrid compound which orders ferromagnetically at TC = 10 K.

Figure 6. Peptide-intercalated layered metal hydroxides: effect of peptide chain length and side chain functionality on structural, optical and magnetic properties.

Fig. 5. Powder XRD patterns of Ni((R,R)CySalenSO3)ÌCu (3) (green) and Ni((R,R)CySalenSO3)ÌCo (5) (purple) (Cu Kα1 = 0.1540598 nm) and structural model. The optical circular dichroism (CD) spectra of the hybrid compounds showed that the chirality of the complex was retained when grafted into the inorganic lamellar host (Fig. 7). Hence, the insertion of the chiral nickel complexes actually enables to donate the hybrid compounds its chiral character.

Figure 7. The post modification strategy.