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Thiol-ligand exchange to form either 1D luminescent or 2D non-emissive Ag(i)-based coordination polymers.

A hydrolytically stable metal–organic framework containing Ti(iv) and porphyrinic linkers allows a photoinduced charge separation process for the photocatalytic overall water splitting reaction.

Solventless synthesis and processing of Metal Organic Frameworks (MOFs) is critical to implement these materials in applied technologies. Vapour phase synthesis of MOF thin films is particularly suitable for such applications, but challenging compared to the conventional solution based methods. It is therefore compelling to advance and widen the vapour phase synthesis of MOF thin films. Crystalline copper terephthalate MOF thin films are grown in the vapour phase by means of atomic and molecular layer deposition (ALD/MLD) on different kinds of substrates. Expanding from the pioneering work, the formation of the 3D phase is clearly evidenced for the first time and the adaptability of the process to several kinds of substrates is revealed. A directional film growth is observed at the early stage of the ALD/MLD process leading to oriented MOF crystallites on a surface, when isotropical growth proceeds with the increasing number of ALD/MLD cycles. Notably, this study primarily demonstrates a heteroepitaxial growth achievable in the vapour phase by using DMOF-1 single crystals as the starting surface with a lattice matching topology. Such an approach offers an appealing pathway to develop MOF on MOF superlattice materials in the vapour phase.

We describe a simple bottom-up strategy to generate [Au(SPh)]n (SPh: thiophenolate) coordination polymer (CP) based thin films by employing an interfacial self-assembly on a nylon substrate. This m...

SSCI-VIDE+CDFA+ADM; International audience; Gold thiolate coordination polymers (CPs) are anisotropic materials with 1D or 2D networks exhibiting a large palette of photoluminescence properties. In this paper, we show that, from both lamellar acid and ester, [Au(p-SPhCO2X)]n CPs (X = H, Me), it is possible to perform post-synthesis esterification or saponification reactions. Three new 2D phases with X = Na, K and Cs were isolated. In addition, ligand exchange reactions were carried out from 1D [Au(p-SPh)]n CP and 2D [Au(p-SPhCO2X)]n CPs (X = H, Me) and the transformations from 1D to 2D structures and vice versa point out a mechanism of dissolution and recrystallization that is governed by the nature of the ligands and the presence of weak interactions. The obtained compounds exhibit solid state and RT photoemission characteristic of their structure.

A neutral coordination polymer made of Ag(i) and 1,3-benzenedithiolate, [Ag2(1,3-BDT)]n, displays both photoluminescence properties and a second harmonic generation signal.

International audience; Given the ubiquitous role of porphyrins in natural systems, these molecules and related derivatives such as phthalocyanines are fascinating building units to achieve functional porous materials. Porphyrin-based MOFs have been developed since the past three decades, yet chemically robust frameworks, necessary for applications, have been achieved much more recently and this field is expanding. This progress is partially driven by the development of porphyrins and phthalocyanines bearing alternative coordinating groups (phosphonate, azolates, phenolates…) that allowed to move the related MOFs beyond metalcarboxylates and achieve new topologies and properties. In this perspective article we first give a brief outline of the synthetic pathways towards simple porphyrins and phthalocyanines bearing these complexing groups. The related MOF compounds are then described; their structural and textural properties are discussed, as well as their stability and physical properties. An overview of the resulting nets and topologies is proposed, showing both the similarities with metal-carboxylate phases and the peculiarities related to the alternative coordinating groups. Eventually, the opportunities offered by this recent research topic, both in term of synthesis pathways, modulation of pore size and shape, stability and physical properties, are discussed

International audience; Here we show that nonanuclear lanthanide complexes respresent a new class of solution state upconversion (UC) molecules. For a composition of one Tb per eight Yb the nonanuclear complexes display a very efficient UC phenomenon with Tb luminescence in the visible region upon 980 nm NIR excitation of Yb. An unprecedented value of 1.0 × 10−7 was obtained for the UC efficiency at only 2.86 W cm−2, demonstrating these new molecular complexes to be up to 26 times more efficient than the best current molecular systems, the UC being observed down to a concentration of 10 nM.

Up until now restricted to solid state chemistry and nanoparticles, upconversion (UC) phenomena by which low energy photons are piled up to engender higher energy emission, are progressively entering the field of molecular probes with a handful of molecular/supramolecular discrete complexes. Here we show that nonanuclear lanthanide complexes respresent a new class of solution state UC materials, and are straightforwardly crystalized from LnCl3.6H2O salts, triethylamine and acetylacetone, retaining their structural integrity in solution. For a composition of one Tb per eight Yb the nonanuclear clusters display a very efficient upconversion phenomenon with Tb luminescence in the visible region upon 980 nm NIR excitation of Yb. An unprecedented value of 1.0×10-7 was obtained for the UC efficiency at only 2.86 W/cm2, demonstrating these new molecular clusters to be up to 26 times more efficient than the best current molecular systems, the UC being observed down to a concentration of 10 nM.

Though Metal Organic Frameworks (MOF's) and MOF-derived solids have been employed in various applications, especially catalysis, there is still a constant search for better performing MOF-based hybrid catalysts. In this work, we employed sacrificial template method in synthesizing MIL-53(Al) type - porous Alumina (MA) composites that exhibit different physico-chemical and catalytic properties compared to parent solids (MIL-53 and mesoporous Al2O3). Structural investigations demonstrated that composites possess combined structure of both the parent solids. Novel composites possess hierarchical (meso- & micro-) pores, with average pore width in the range of ~14–16 nm. NH3 adsorption calorimetry and isopropanol test enabled deducing the possible nature and strength of acid-basic sites in composites. ‘MA’ composites show intermediate chemical properties and synergistic multifunctional catalytic behaviour compared to parent solids. This work reveals, for the first time, extensively tunable physico-chemical properties of a novel class of solids: “the MIL-53(Al) type - porous alumina composites” that can have a huge potential as multifunctional catalysts.

International audience; Vapor-phase infiltration (VPI), a technique derived from atomic layer deposition (ALD) and based on sequential self-limiting chemistry, is used to modify the stable microporous porphyrin-based metal–organic framework (MOF) MIL-173(Zr). VPI is an appealing approach to modifying MOFs by inserting reactants with atomic precision. The microporous nature and chemical stability of MIL-173 enable postsynthesis modification by VPI without MOF degradation even with extremely reactive precursors such as trimethylaluminum (TMA) and diethylzinc (DEZ). VPI proceeds through the diffusion of gaseous organometallic reactants TMA and DEZ inside the microporous framework, where they react with two kinds of chemical sites offered by the porphyrinic linker (phenolic and pyrrolic functions in the porphyrin core), without altering the crystallinity and permanent porosity of the MOF. 27Al NMR, UV–vis absorption, and IR spectroscopies are used to further characterize the modified material. Physisorption of both precursors is computationally simulated by grand canonical Monte Carlo methods and outlines the preferential adsorption sites. The impact of temperature, number of VPI cycles, and pulse length are investigated and show that aluminum and zinc are introduced in a saturating manner inside the MOF on both available reactive sites. The porosity prerequisite is outlined for VPI, which is proven to be much more effective than classical solution-based methods because it is solventless and fast, prevents workup steps, and allows reactions not possible by the classical solution approach.

International audience; Shaping of functional materials is of tremendous importance for applications. Among coordination polymer compounds, one of the challenges is to get fibers that can be self-standing and flexible, while maintaining their crystallinity and properties. Here, the synthesis and characterization of free-standing fibers of a Au(I)-based coordination polymer (CP) are reported. The flexible fibers of the 1D gold(I)–thiophenolate [Au(SPh)]n CP have an average diameter of 270 nm and length of a few micrometers. They are hydrophobic because of the presence of phenyl rings and exhibit high chemical stability in harshly acidic and basic conditions due to the strong Au(I)–S interactions. These fibers are red-emissive at room temperature because of the presence of aurophilic interactions. In addition, a composite material can be easily obtained through calcination, resulting in the formation of gold nanoparticles (AuNPs) on the CP fiber surface. Owing to the plasmonic resonance of AuNPs, this composite material exhibits good sensitivity towards the detection of molecules as observed through surface enhanced Raman scattering (SERS).

The structure of a new lamellar gold thiolate coordination polymer is described. [Au(+I)(p-SPhCO2H)]n exhibits unique bent S–Au–S angles due to the presence of both aurophilic and hydrogen interactions. More interestingly, this compound is the first coordination polymer displaying intrinsic dual emission in a large temperature range, from 80 to 320 K, with a maximum sensitivity of 3% K−1 at 260 K, and it possesses high potential as an optical temperature sensor.

The use of a 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin has yielded a new MOF based on M-1,2,3-trioxobenzene chains that can be made of M = Zr(iv) or RE(iii) (RE = rare earth), showing a very high and limited chemical stability, respectively. The robust metallated Zr-analogue, Co-MIL-173(Zr), has proven to be a heme-like heterogeneous catalyst suitable for aerobic oxidation of hydrocarbons.

SSCI-VIDE+CDFA+ADM; International audience; Two new 3D porphyrin-based metal organic frameworks were obtained by solvothermally reacting iron(III) chloride, a free base (5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl) phenyl] porphyrin) (H2TTPP) and either pyrazine or 1,4-diazabicyclo[2.2.2] octane (DABCO). Both MOFs displayed a 3-D open framework of the fry topology, where the inorganic building unit is a chain of corner-sharing FeN4O2 octahedra and the porphyrinic linker is metallated with iron during the reaction course, with the N-donor base bridging the iron of the porphyrinic cores. Through thorough structural and spectroscopic analyses of the pyrazine containing material the chemical formula [Fe(II)pzTTP(Fe-1-x(II) (DMF1-xFexOHx)-O-III)](n) was inferred (x >= 0.25). Whereas the already reported carboxylate analogue is built up from a pure iron(III) inorganic chain, here spectroscopic and structural studies evidenced a mixed valence iron(II/III) state, evidencing that, in agreement with the HSAB theory, the substitution of a carboxylate function by a tetrazolate one allows redox tuning. Finally, both materials feature one-dimensional channels of ca. 8 x 12 angstrom within the structures with permanent microporosity.

The photoluminescence of gold thiolate clusters brings about many potential applications, but its origin is still elusive because of its complexity. A strategy in understanding the structure&ndash, properties relationship is to study closely related neutral gold thiolate coordination polymers (CPs). Here, a new CP is reported, [Au(m-SPhCO2H)]n. Its structure is lamellar with an inorganic layer made of Au&ndash, S&ndash, Au&ndash, S helical chains, similar to the [Au(p-SPhCO2H)]n analog. An in-depth study of its photophysical properties revealed that it is a bright yellow phosphorescent emitter with a band centered at 615 nm and a quantum yield (QY) of 19% at room temperature and in a solid state. More importantly, a comparison to the para-analog, which has a weak emission, displayed a strong effect of the position of the electron withdrawing group (EWG) on the luminescent properties. In addition, [Au(m-SPhCO2H)]n CPs were mixed with organic polymers to generate transparent and flexible luminescent thin films. The ability to tune the emission position with the appropriate contents makes these nontoxic polymer composites promising materials for lighting devices.

The reactivity of two phenolic porphyrins bearing respectively catechol and gallol-derived meso substituents (5,10,15,20-tetrakis(3,4-dihydroxyphenyl)porphyrin and 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin) with trivalent metallic ions (Fe, Mn, In) was studied. Six supramolecular compounds were obtained and structurally characterized by single crystal X-ray diffraction. In each compound, the supramolecular assembly was based on the axial coordination of a phenolate function to the metallic ion lying in the porphyrinic core. A great diversity of supramolecular architectures was accessible through such simple arrangements, and objects ranging from dimers to one-dimensional polymers were isolated. Some of these assemblies were further investigated in solution by mass spectrometry and by UV-vis absorption spectroscopy. For the iron-based materials, the redox behavior was studied in solution through cyclic voltammetry experiments in inert conditions and under air.

SSCI-VIDE+CDFA:ECI2D+OVE:DEC:ADM; International audience; The structures of two lamellar silver thiolate coordination polymers [Ag(p-SPhCO2H)]n (1) and [Ag(p-SPhCO2Me)]n (2) are described for the first time. Their inorganic part is composed of distorted Ag3S3 honeycomb networks separated by noninterpenetrated thiolate ligands. The main difference between the two compounds arises from dimeric hydrogen bonds present for the carboxylic acids. Indepth photophysical studies show that the silver thiolates exhibit multiemission properties, implying luminescence thermochromism. More interestingly, the synthesis of a heterometallic lamellar compound, [Ag0.85Cu0.15(p-SPhCO2H)]n (3), allows to obtain mixed metal thiolate coordination polymers and to tune the photophysical properties with the excitation wavelengths from a green vibronic luminescence to a single red emission band.

Five Tb3+/Eu3+ mixed nonanuclear clusters with the general formula [Eu9–xTbx(acac)16(µ3-OH)8(µ4-O)(µ4-OH)] ([Eu9–xTbx], x = 0.9–8.1, acac = acetylacetonate) were synthesized. Characterization by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS) and inductively coupled plasma optical emission spectroscopy (ICP-OES) highlight a near-perfect match between the amounts of Tb3+ and Eu3+ ions input in the reaction mixture and the amounts in the clusters. The luminescence properties of these [Eu9–xTbx] clusters were investigated thoroughly in the solid state, and a strong energy transfer from the Tb3+ to Eu3+ emitters was evidenced. Thus, these nano-nonanuclear 4f clusters, which can be viewed as square pyramids that share one top, exhibit dual luminescence that can be adjusted by controlling the ratio of the lanthanide ions within the crystal architecture.

The catalytic properties of a chemically stable iron porphyrin MOF were evaluated in a reaction with ethyl diazoacetate. In contrast to its homogeneous counterpart, an Fe-porphyrin-MOF features a different reaction pathway leading to the formation of pyrazoline due to the confinement of catalytic sites within the MOF network. Unexpectedly, a sharp increase of the selectivity from 35% (run 1) to 86% (run 5) occurs upon catalyst recycling.

SSCI-VIDE+CDFA+CLA:LOK:MMO:ADM; International audience; A gold(I)-thiophenolate coordination polymer, [Au(SPh)](n), has been synthesized by employing hydrothermal conditions at 120 degrees C. This new synthesis led to isolate highly crystalline compound and to solve its structure from powder X-ray diffraction patterns. The compound forms double interpenetrated helical chains stabilized through C-H center dot center dot center dot pi and aurophilic bonds. The solid is phosphorescent at room temperature and in the solid-state with a quantum yield of around 5%. Thanks to DFT calculations, the emission is attributed to a Ligand-to-Metal-Metal Charge Transfer (LMMCT) transition with a small contribution from a Metal Centered (MC) transition. In addition to this hydrothermal reaction, it is possible to obtain this [Au(SPh)] n coordination polymer by a two-step synthesis which is a thermally-induced solid-state amorphous-to crystalline isomerization. This transition has been followed by powder X-ray diffraction, scanning electron microscopy, differential scanning calorimetry and also from the appearance of phosphorescence upon heating.

XPS+CDFA+ADM:LCS; International audience; Metal Organic Frameworks (MOFs) have been recently proposed as promising electrocatalysts, yet the exact nature of the mechanisms in play has not been addressed in depth. By comparing the electrocatalytic activity of a MOF for the oxygen reduction reaction (ORR) and the corresponding molecular building units through electrochemical techniques, here, we investigate the nature of the catalytic sites, their redox states and the electron transfer pathways.

A copper thiolate coordination polymer, [Cu(p-SPhCO2Me)]n, is described and exhibits, under UV, luminescence thermochromism, associated to a unique well-separated triple emission. This compound is the most promising candidate as a ratiometric temperature sensor, working in a wide temperature range, from 100 to 500 K, with a great sensitivity.

International audience; This review article presents the fundamental and practical aspects of water adsorption in Metal-Organic Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aqueous media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.

A porphyrin-based metal-organic framework is shown to be structurally stable towards acid loading using either hydrochloric or formic acid. The capacity of this material as an ammonia sorbent was analysed using micro-breakthrough experiments in both dry and humid ammonia flows. The acid loaded material exhibited excellent uptake in comparison with the parent MOF.

SSCI-VIDE+CDFA+CLA:MMO:ADM; International audience; The first structure elucidation of a lamellar gold thiolate coordination polymer is described. [Au(p-SPhCO2Me)](n) is obtained from the simultaneous esterification of mercaptobenzoic acid and reduction of the Au(III) precursor. Despite the presence of aurophilic interactions, the intense phosphorescence (QY similar to 70%) originates from intra-ligand and metal-to-ligand transitions.

The coordination of benzene-1,3,5-tribenzoate (BTB) and imidazole (Im) with cobalt under basic conditions yields a 2D layered structure, Co 3 (BTB) 1.5 (Im) 1.35 (O) 0.5 (OH) 0.5 (H 2 O) 1.65 guests ( 1 ), in which the imidazoles are weakly π–π stacked and hydrogen bonded to the adjacent layers affording a 3D supramolecular network. The structure is based on a hexanuclear Co 6 building unit which comprises four octahedral and two tetrahedral Co(II) centres. The framework is permanently porous to N 2 , CO 2 and CH 4 , with the strength of interaction at zero coverage being comparable to that at high loading.

A new series of 3-D coordination polymers based on iron(III) and nickel(II) tetracarboxylate porphyrin (Ni-TCPP) have been produced using solvothermal conditions. MIL-141(A) solids (MIL stands for Material from Institut Lavoisier), formulated Fe(Ni-TCPP)A•(DMF)x (A = Li, Na, K, Rb, Cs, DMF = N,N-dimethylformamide, x ∼ 3), are built up from three anionic interpenetrated PtS-type networks charge-balanced by alkali cations (A) entrapped inside the pores. MIL-141(A) thus includes three types of cations, two of which may act as coordinatively unsaturated metal sites (Ni2+ and A+). These solids all present a permanent porosity with a reasonably high surface area (SBET = 510–860 m2 g–1) as well as some structural flexibility toward adsorption/desorption processes, modulated in both cases by the nature of A. Thermally Stimulated Current (TSC) measurements indicated that alkali cations are rather homogeneously distributed within the pores, while their interaction with the framework is stronger in MIL-141(A) than i...

We describe the synthesis of a new family of chiral bridled porphyrins. They were obtained by reaction between pyrrole and a chiral 2-formylcyclohexanol derivative. Thanks to an enzymatic kinetic resolution method, these compounds were obtained in both enantiomeric forms. This resolution method allows easy synthesis of chiral precursors in high yield and on large scale. These new porphyrins exhibited an (αα)(αα) conformation and the less usual (αα)(ββ) one, depending of the bridle length.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Reaction of iron(IIII)chloride with the free base tetrakis(4-carboxyphenyl)porphyrin (H2TCPP) in the presence of different bases leads to the formation of a series of iron/porphyrin metal–organic frameworks. Such a crystal engineering approach led to the obtaining of four structures presenting three different topologies and inorganic secondary building units. Depending on the synthesis conditions, isolated FeIII octahedra, diiron(II) paddle wheel dimers, or extended [FeIII(OH)O4]n chains could be obtained in a controlled manner. The influence of the synthetic conditions on the final structure and the oxidation state of iron is discussed. Stability of the porous solids towards air and water is studied, and their intrinsic porosity is assessed.

The adsorption of benzene in the cation-containing metal–organic framework (MOF) MIL-141(Cs) was explored by manometry measurements coupled with Monte Carlo simulations. This joint experimental/modeling approach demonstrates that this solid shows a high affinity for benzene that does not result from a direct interaction between the guest molecules and the Cs+ cations, in contrast to what is commonly observed in zeolites. This behavior was attributed to the high degree of confinement of Cs+, which prevents any cation detrapping upon adsorption, as revealed by dielectric relaxation spectroscopy and molecular dynamics simulations. This peculiar adsorption behavior is further discussed in relation to that of other alkali extraframework cations including Li+, Na+, K+, and Rb+.

A new porous Fe III -based MOF, formulated Fe(OH)(BDC)• (dmf) x with x ≈ 1.1 and presenting the MIL-68 topology, was prepared by reaction of an iron(III) salt and terephthalic acid (H 2 BDC) in N,N'-dimethylformamide (dmf) under acidic conditions. The structure and properties of this solid were studied by means of X-ray diffraction, thermogravimetric analysis, nitrogen sorption, 57 Fe Mossbauer spectrometry, and electrochemical lithium insertion.

We describe a method to improve the yield and the kinetics of the difficult syntheses of α,β-unsaturated porphyrins, which enabled us to obtain a new chiral porphyrin derived from (S)-(−)-perillaldehyde in a 6% yield. Variable temperature NMR experiments on the free base, the zinc(II) and the nickel(II) complexes showed that two distinct and consecutive dynamic processes linked with the meso substituents rotation occurred. These processes can be analyzed as an evolution of the conformer composition upon temperature change. Higher values are found for the free energies of rotation of the substituent (measured by variable temperature 1H NMR) compared to those of other equivalent porphyrins like meso-tetraphenyl porphyrin or meso-tetracyclohexyl porphyrin.

For the past ten years, there has been considerable interest dedicated to the miniaturisation of CMOS devices. The research axes followed to obtain scalable devices are numerous as the possibilities offered by both technological (top-down) and new (bottom-up) approaches are studied. Concerning the latter approach molecular electronics is a growing field of interest. Notably, the fabrication of hybrid molecule/Si structures paves the way for development of devices with electrical performances that can be tuned thanks to the molecular properties initially targeted. Here we present the recent results obtained in the two approaches we follow in order to develop new hybrid molecule/Si memory elements. The first axis focuses on the development of specific molecules that could allow a fine tuning of the memory retention characteristic. The second axis deals with the integration of redox molecules inside capacitive cells and the study of their electrical properties. The capacitance of such components clearly shows that an effect of charge transfer is observed only when redox active molecules (porphyrins) are grafted on Si.

The discovery of a universal memory that exhibits fast access speed, high-density storage, and non-volatility has fuelled research into phase-change materials over the past decades. In spite of the efficiency of the inorganic chalcogenides for phase-change random access memory (PCRAM), they still have some inherent drawbacks, such as high temperature required for phase change and difficulty to control the domain size of the phase change, because of their brittleness. Here we present a Au

Over the last few decades, lanthanides have been highlighted in high technology. These elements are used in strategic applications such as optical glasses and lasers, telecommunications, lighting and screens, magnetic materials, hard drive, security inks and counterfeit labels, catalysis, biosciences and medicine…This progress makes the coordination chemistry of 4f elements a mature and attractive field of research with almost unlimited perspectives which brings a new perception, a new area to coordination chemistry. The quest for new materials to improve the character provided by the 4f elements is steadily intensifying. In this context, the precise understanding of the structure-property relationship takes an important place, since this latter derives the properties. Consequently, it is still necessary to design new structures to expand the available database and thus improve knowledge and then promote applications. The present work is part of this idea to provide more information on the structure-properties relationship of lanthanide complexes. Indeed, during this thesis different original nuclear systems were developed and we were particularly interested in the description and understanding of the magnetic and luminescence properties. Molecular entities were constructed with β-diketone ligands. The latter offer different modes of coordination that have allowed the design of new families of lanthanide complexes. According to synthesis conditions, the nuclearity of the complexes is controlled from [Ln1] to [Ln9]. By doping the complexes with high nuclearity we were able to exacerbate the luminescence properties of the compounds studied. In regards to magnetism, the dinuclear, trinuclear and tetranuclear structures exhibit a single molecule magnet (SMM) behavior and some are magnet molecules with a toroidal moment. Other such complexes can also behave as bi-functional materials, combining SMM and luminescent property. Thus the study of the spectroscopic and magnetic character of these entities enabled us to rationalize the physical properties with respect to the structure, which is a great advantage in the field of coordination of the lanthanides; Au cours de ces dernières décennies, les cations lanthanides trivalents ont été à l'honneur en matière de haute technologie. Ces éléments sont utilisés dans des applications stratégiques telles que les lunettes optiques et les lasers, les télécommunications, l'éclairage et les écrans, les matériaux magnétiques, les disques durs, les encres de sécurité et les labels de contrefaçon, la catalyse, les biosciences et la médecine, pour n'en citer que quelques exemples. Cet intérêt croissant pour ces métaux fait de la chimie de coordination des éléments 4f un champ de recherche attrayant avec des perspectives presque illimitées. Ainsi la quête de nouveaux matériaux afin d'améliorer le caractère apporté par les éléments 4f au sein de complexes moléculaires n'a cessé de s'intensifier au cours des dernières décennies. Dans ce cadre, la compréhension précise de la relation structure cristalline-propriétés physiques (magnétisme, luminescence) devient primordiale puisqu'elle permet d'améliorer les objets synthétisés. Par conséquent, la conception de nouvelles architectures moléculaires à base d'ions lanthanide se révèle être nécessaire pour élargir la base de données disponibles et ainsi améliorer les connaissances pour ensuite optimiser les applications. Le présent travail de recherche s'insère parfaitement dans cette thématique, à savoir améliorer les connaissances sur les corrélations possibles entre la structure cristalline d'un complexe d'ions lanthanide et ses propriétés. Au cours de cette thèse, différents systèmes moléculaires originaux ont été élaborés et nous nous sommes particulièrement intéressés à la description et la compréhension des propriétés magnétiques et de luminescence. Les complexes ont été construits avec des ligands de type β-dicétone. Ces dernières offrent différents modes de coordinations qui ont permis de mettre en œuvre de nouvelles familles de complexes de lanthanides. Selon les conditions de synthèse, la nuclearité des complexes est contrôlée de [Ln1] à [Ln9]. De même, il a été possible en ajustant les conditions de synthèse de contrôler finement l'environnement des ions lanthanide au sein de ces complexes. Par dopages des clusters à forte nuclearités, nous avons pu exacerber les propriétés de luminescence des composés étudiées. Les édifices dinucléaires, trinucléaires et tétranucléaires présentent quant à eux un comportement de molécule-aimant et certains d'entre eux sont des molécules-aimants avec un moment toroïdal. Enfin, certains de ces complexes peuvent également se comporter comme des matériaux bi-fonctionnels combinant propriété de molécule-aimant et de luminescente. Ainsi l'étude du caractère spectroscopique et magnétique de ces entités nous a permis de rationaliser les propriétés physiques par rapport à la structure

Porphyrins are important macrocyclic compounds which are prevalent in nature and have been extensively studied by chemists in homogeneous catalysis as enzyme mimics. Incorporating porphyrins in metal-organic frameworks (MOFs) offer an ideal opportunity to obtain material with extended frameworks possessing the same properties as the homogenous systems. Much work has been done on porphyrinic MOFs but their stability remains a problem and a major limitation for possible wide scale applications. In literature, more stable MOFs have been realised using high valent metal ions in the inorganic building unit (such as Fe3+, Al3+, Zr4+) and/or by using more basic functionalities in the organic linker. However, regarding porphyrinic MOFs, little work is reported with ligands based on functionalities other than carboxylic acid groups. Therefore, our work focused on investigating the reactivity of porphyrinic ligands carrying various functionalities with high valent metal ions. More precisely, we focused on the design, synthesis optimisation and characterisation of such materials. This included studying existing stable carboxylate porphyrinic frameworks with a goal of incorporating new functionalities, which led to new variations of these materials. Our work also demonstrated that the framework topologies observed with carboxylate based porphyrinic ligand can be expanded to other functionalities with the synthesis of a new tetrazolate based porphyrinic MOF. MOF synthesis was also investigated with phenolate functionalised ligands and resulted in the first gallate based porphyrinic MOF reported. The stability of this new material was assessed. This manuscript discusses the synthesis and the characterisation of these MOFs via a combination of experimental techniques (X-ray diffraction, TGA analysis, UV-vis spectroscopy, IR-spectroscopy, sorption studies etc.). The preliminary evaluation of the catalytic activity of some of the MOFs is also described, Les porphyrines sont des composés macrocycliques naturels étudiés de manière approfondie en tant que mimétiques enzymatiques ou catalyseurs d'oxydation en milieu homogène. L'incorporation de porphyrines dans des réseaux de polymères de coordination métal-organique (MOFs), qui constituent une famille de composés cristallins poreux connus pour leur diversité structurelle, pourrait conduire à des matériaux constitués de réseaux étendus présentant les mêmes propriétés que les systèmes homogènes. Toutefois de nombreux travaux ont montré que la limitation majeure pour des applications à grande échelle des MOFs est leur stabilité.La stabilité de ces matériaux peut être accrue en employant des cations métalliques de valence élevée dans l'unité de construction inorganique (tels que Fe3+, Al3+, Zr4+) et / ou en modifiant la fonction coordinante du ligand organique.Ce travail est relatif à l'étude de la réactivité de ligands porphyriniques portant diverses fonctions coordinantes, avec des ions métalliques de valence élevée. L'influence des paramètres de synthèse et la caractérisation approfondie de ces MOFs ont été réalisées par une combinaison de techniques expérimentales (diffraction des rayons X, analyse thermogravimétrique, spectroscopie UV-vis, spectroscopie infrarouge, études de sorption, etc.). Dans un premier temps, l'étude s'est focalisée sur des MOFs porphyriniques à base de groupements carboxylates stables connus, ce qui a conduit à de nouvelles variantes de ces matériaux. Dans un second temps il est démontré que les topologies des réseaux observées sur un ligand porphyrinique à base carboxylate peuvent être étendues à d'autres fonctionnalités avec la synthèse d'un nouveau MOF à base de tétrazolate. L'amélioration de la stabilité a également été explorée avec des ligands portant des fonctions phénol qui ont abouti à l'élaboration de nouveaux réseaux de coordination. La synthèse et l'étude de stabilité d'un MOF porphyrinique à base de gallate est rapportée. L'évaluation préliminaire de l'activité catalytique de certains des MOFs élaborés est également décrite