Auswahl der wissenschaftlichen Literatur zum Thema „Polyfunctional ligand“

Manganese(IV) complexes viz. [MnIV(nagh)(A)2]·2H2O and [MnIV(nagh)(NN)] have been synthesized from ligand bis(2-hydroxy-1-naphthaldehyde)glutaryldihydrazone (naghH4) and auxiliary ligands, A = H2O (1)/pyridine (2)/2-picoline (3)/3-picoline (4)/ 4-picoline (5) or NN = 2,2′-bipyridine (6)/1,10-phenanthroline (7). The elemental analysis, mass spectral and thermal studies supported the composition of all the manganese(IV) complexes. Structural aspects were determined from magnetic susceptibility, molar conductivity and spectral studies i.e. electronic, electron spin resonance and infrared. Their non-electrolytic nature were determined from molar conductances. Results from studies of magnetic moment, electronic and ESR suggested Mn(IV) ion in six-coordinate octahedral stereochemistry. The ligand coordinated to the metal in enolic form as a tetradentate in an anti-cis configuration as was correlated from IR data. Redox activities and antimicrobial potential against few Gram-positive and Gram-negative bacteria have been investigated for the dihydrazone and some manganese(IV) complexes.

Abstract MEM-288 is a dual-transgene armed oncolytic adenovirus in phase 1 clinical development as a standalone agent and in combination with immune checkpoint inhibitors (ICI). It encodes two potent immune agonists: IFNβ and a recombinant membrane-stable chimeric form of CD40L (MEM40). We previously demonstrated this agonist combination is better than either agonist individually to activate conventional dendritic cells type 1 (cDC1) crucial for CD8+ T cell cross-priming, and to increase tumor-antigen reactive CD8+ T cells. Furthermore, first-in-human Phase 1 clinical trial (NCT05076760) results of MEM-288 for advanced non-small cell lung cancer (NSCLC) and other solid tumors showed MEM-288 tumor shrinkage was associated with systemic antitumor T cell immunity as demonstrated by cytokine, T cell clonotype, and tumor neoantigen analysis. Here, we investigated the precise nature of the localized and systemic T cell response induced by MEM40 + IFNβ in preclinical tumor models. Single-cell RNA sequencing of tumor infiltrating T lymphocytes (TILs) revealed that MEM40 + IFNβ elicited a strong increase in T cells expressing Granzyme B and PRF1, key effector cytokines and cytotoxicity mediators. We tracked the CD8+ T cell response in CD45.1 C57BL/6 mice implanted with syngeneic B16 tumor expressing the model antigen OVA. Interestingly, intratumoral treatment with adenovirus encoding MEM40 + IFNβ did not cause an appreciable increase in absolute numbers of antigen-reactive CD8+ T cells, despite tumor growth inhibition. However, MEM40 + IFNβ compared to control unarmed adenovirus induced a significant (p < 0.005) 5-fold increase in polyfunctional IFNγ+TNFα+PRF1+ and IFNγ+TNFα+Granzyme B+ CD8+ T cells. Polyfunctional CD8+ T cells have the capacity to simultaneously produce effector cytokines and cytotoxicity mediators and are known to be strongly associated with antitumor T cell activity. The robust polyfunctional CD8+ T cell response in these studies is consistent with T cell-driven antitumor activity found in both our preclinical tumor experiments and our clinical studies in advanced NSCLC patients responding to MEM-288. Overall, our findings suggest MEM40 + IFNβ generates a strong polyfunctional CD8+ T cell response in the TME that warrants continued evaluation to understand the pleiotropic mechanisms of this cancer immunotherapy. Citation Format: Mark J. Cantwell, Andreas N. Saltos, Hong Zheng, Dana Foresman, Amer A. Beg. Oncolytic adenovirus dually expressing interferon beta and membrane-stable CD40 ligand increases polyfunctional CD8+T cells associated with antitumor activity [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 6655.

A series of mononuclear manganese(IV) complexes of disalicylaldehyde fumaroyldihydrazone (slfhH4) were synthesized by reacting manganese acetate tetrahydrate with dihydrazone in absence and presence of various pyridine bases in methanol medium. Pyridine (py) and its derivatives like 2-picoline (2-pic), 3-picoline (3-pic), 4-picoline (4-pic), 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) were added to the reaction mixture of metal salt and dihydrazone to explore the binding possibilities of these molecules to manganese center. The elemental analysis, mass spectral and thermal studies were used to derive their composition. Study of magnetic moment, molar conductances, electronic, EPR and infrared spectroscopy have led to interpretation of their tentative structures. Magnetic moment and EPR studies correspond to their Mn(IV) oxidation state. The dihydrazone functions as tetradentate ligand chelating the manganese(IV) ion present in octahedral geometry with anti-cis configuration in enol form. Electrochemical and antimicrobial studies were also performed.

DNA vaccines offer promising strategies for immunization against infections. However, their clinical use requires improvements in immunogenicity. We explored the efficacy of Toll-like receptor (TLR) ligands (TLR-Ls) on augmenting the immunogenicity of a DNA prime–modified vaccinia virus Ankara (MVA) boost vaccine against SIV. Rhesus macaques were injected with Fms-like tyrosine kinase 3 (Flt3)–ligand (FL) to expand dendritic cells (DCs) and were primed with a DNA vaccine encoding immunodeficiency virus antigens mixed with ligands for TLR9 or TLR7/8. Subsequently, the animals were boosted with DNA and twice with recombinant MVA expressing the same antigens. TLR9-L (CpG DNA) mediated activation of DCs in vivo and enhanced the magnitude of antigen-specific CD8+ interferon (IFN) γ+ T cells and polyfunctional CD8+ T cells producing IFN-γ, tumor necrosis factor α, and interleukin 2. Although this trial was designed primarily as an immunogenicity study, we challenged the animals with pathogenic SIVmac251 and observed a reduction in peak viremia and cumulative viral loads in the TLR9-L plus FL-adjuvanted group relative to the unvaccinated group; however, the study design precluded comparisons between the adjuvanted groups and the group vaccinated with DNA/MVA alone. Viral loads were inversely correlated with the magnitude and quality of the immune response. Thus, the immunogenicity of DNA vaccines can be augmented with TLR9-L plus FL.

The synthesis and structure elucidation of a new series of manganese(IV) complexes from disalicylaldehyde glutaryldihydrazone (slghH4) of the composition [MnIV(slgh)](A)2]·H2O and [MnIV(slgh)(NN)] (where A= H2O, (1); pyridine, (2); 2-picoline, (3); 3-picoline, (4); 4-picoline, (5) and NN = 2,2′-bipyridine, (6); 1,10-phenanthroline, (7)) were carried out. The composition and structures of all the complexes of Mn(IV) have been evaluated by elemental analysis, thermal studies, molar conductance, mass spectral data, magnetic moment, electronic, electron paramagnetic resonance and infrared spectral studies. Molar conductances of these Mn(IV) complexes suggest their non-electrolytic nature. Magnetic moment and EPR studies suggested that the Mn(IV) ions are six-coordinated octahedral geometry around the metal ions. The IR spectral studies confirmed that the ligand coordinates to the Mn(IV) ion in enolic form and behave as a tetradentate ligand in anti-cis configuration chelating Mn(IV) ion with NNOO coordination sites. The electrochemical and antimicrobial studies of the Mn(IV) complexes have also been carried out.

Исследовано комплексообразование европия и тербия с полифункциональными органическими соединениями – β-дикетонами, органическими кислотами. Состав комплексов изучен экстракционным методом, ИК и люминесцентной спектроскопией. Установлено, что при экстракции РЗЭ смешанными экстрагентами идет эффективное комплексообразование РЗЭ в органической фазе. Показана возможность синтеза из насыщенных экстрактов разнолигандных координационных соединений РЗЭ, выделены индивидуальные кристаллические комплексы. The complex formation of europium and terbium with polyfunctional organic compounds: β-diketones, organic acids were investigated. The composition of the complexes was studied by extractive method, infrared and luminescent spectroscopy. It was established that during the extraction of REE by mixed extractants there is an effective complex formation of REE in the organic phase. The possibility of synthesis of different ligand coordination compounds of REE from saturated extracts was shown and individual crystalline complexes were isolated.

Abstract Our ongoing interest in the chemistry of polyfunctional Lewis acids has led us to investigate the reaction of the stibonium-borane [o-(Ph2MeSb)(Mes2B)C6H4]+ (1+) with cyanide and azide, two toxic anions. Both anions react with 1+ to afford the corresponding neutral complexes 1-CN and 1-N3. Structural and computational studies show that the coordinated anion interacts with both the boron and antimony atoms of the bidentate Lewis acid. While the azide complex features a typical κ2N1 : N1 bridging azide ligand, the cyanide complex possesses a cyanoborate moiety whose cyanide interacts side-on with the stibonium center. The Lewis acid-anion interactions observed in these complexes have also been studied computationally using the Natural Bond Orbital method

Abstract Selectin-selectin ligand interactions mediate the initial steps in leukocyte emigration, an integral part of immune response. Fucosyltransferase-VII (FucT-VII) enzyme, encoded by Fut7 gene, is essential for post-translational modification and function of selectin ligands. In an established model of cardiac allograft vasculopathy and chronic rejection, Fut7-/- recipients, with impaired selectin-dependent leukocyte trafficking, enjoyed long-term graft survival with minimal vasculopathy. This was associated with T cell exhaustion in the periphery characterized by impaired effector cytokine production, proliferative defect, increased expression of inhibitory receptors PD-1 and Tim-3 and low levels of IL-7Ra on CD4 T cells and reduced trafficking of polyfunctional CD4 memory T cells to the allograft. Blocking PD-1, triggered rejection only in Fut7-/- recipients, whereas depleting regulatory T cells triggered rejection in WT recipients. Adoptive transfer experiments confirmed that the exhausted phenotype is seen primarily in CD4 T cells with impaired trafficking ability. In summary, these data suggest that impaired leukocyte trafficking is a novel mechanism of CD4 T cell exhaustion and our experimental system serves as an excellent model to study CD4 T cell exhaustion as a dominant mechanism of transplant tolerance. Further, targeting FucT-VII may serve as a promising strategy to prevent chronic allograft rejection and promote tolerance.

This thesis involves the design, synthesis and testing of organic hydrophobic ligands. They would act as co-collectors in froth flotation processes to enhance the recovery of sulfidic minerals which have undergone some oxidation on processing and are not efficiently collected by the commercial reagents used in froth flotation. Strong and selective binding to iron(III) oxide/hydroxide surfaces, e.g. goethite, over unwanted silicaceous material was considered essential criteria for such new cocollectors. A general overview of froth flotation processes is given in Chapter 1 as well as a description of the analytical techniques used in this thesis and the features that the ligands must have to act as co-collectors. On the basis of the strong binding to iron(III) surfaces of the organic ligand Irgacor 419®, used commercially as a corrosion inhibitor for iron, this compound was studied as a potential co-collector. Adsorption isotherms were determined by UV-Vis spectroscopy for two carboxylic acids that may also bind strongly to goethite, the results of which are discussed in Chapter 2. Chapter 3 involves the measurement of the strength of binding of one the most widely used type of collectors for sulfide ores, potassium ethyl xanthate. Complications in the analysis of materials in solution by both ICP-OES and UV-Vis spectroscopy arose due to the instability of potassium ethyl xanthate in solution, making determination and interpretation of isotherms difficult. The determination of adsorption isotherms for 2-mercaptobenzothiazole, which showed weak binding to goethite as well as to silica, and the mode of binding of 2-mercaptobenzothiazole on copper(I) surfaces is reported in Chapter 4. A crystal structure was obtained in which four units of 2-mercaptobenzothiazole bridge two nickel atoms through the nitrogen atom and the exocyclic sulfur and is considered as a model for binding to sulfidic minerals. Chapter 5 looks at the strength of binding to goethite and silica of various hydroxamic acids. Benzohydroxamic acid was initially selected for study since hydroxamates are known to act as collectors for oxidized materials. Unpredictably, benzohydroxamic acid showed strong binding to a goethite surface and did not release any iron from the surface into solution, which would have been predicted due to its known strong chelating abilities to iron(III). The X-ray structure determination of the first example of a dinuclear Fe(III) hydroxamate complex showed this to have -oxo bridge formed by the hydroxamate unit and supports multisite attachment between this ligand and the surface, as suggested by adsoption isotherms. Simple models based on this dinucleating motif provide plausible modes of multisite attachment to a goethite surface. Competitive binding studies provided a way of ranking the ability to bind to goethite of acetohydroxamic acid, which was not suitable for analyses by either ICP-OES or UV-Vis spectroscopy. Of the ligands studied in this chapter acetohydroxamic acid was found to bind most strongly to goethite followed by benzohydroxamic acid. In Chapter 6, the attachment to goethite and silica of a series of phosphonic acids is investigated. All show a very high binding strength to goethite. Froth flotation experiments at a laboratory scale are described in Chapter 7. The types of ligand that showed strong binding to goethite in adsorption isotherms experiments were tested as co-collectors in different ores and conditions. There is not a simple correlation between adsorption isotherm data and flotation performance as co-collectors because other factors, besides strength of binding, affect the system. Benzohydroxamic acid was the ligand that increased the grade/recovery of the process in all the cases studied. Irgacor 419® enhances the grade/recovery curve for Palabora ore and phenyl malonic acid for Kennecott ore. These results support the original proposition that it may be possible to increase the recovery of oxidized particles substantially by using a blend of collectors which includes a compound to target the oxidized sites.

Le but de ce travail de thèse été de développer de nouvelles familles de ligands polyfonctionnels pour étudier, dans un premier temps, leur chimie de coordination vis-à-vis de centres métalliques et dans un second temps, en fonction des espèces formées, leurs propriétés physiques et/ou catalytiques. Les combinaisons potentiellement les plus intéressantes étaient basées sur l’association de sites donneurs connus pour former des liaisons fortes avec les métaux envisagés, comme les phosphines (P-) ou les carbènes N-hétérocycliques (CNHC-), avec des sites donneurs plus labiles, comme une fonction thioéther (S-). Ce type d’association permet l’élaboration de systèmes dits « hémilabiles », qui se sont montrés d’excellents candidats pour des applications en catalyse homogène. Des ligands de type : diaminophosphine/thioéther : P-, P-, S- ont ainsi été développés. Ces ligands ont montré une grande richesse de modes de coordination, dont il a résulté une grande diversité de complexes organométalliques. Les seconds ligands ciblés étaient de type carbènes N-hétérocycliques (NHC), portant soit un groupement thioéther sur un des atomes d’azote du cycle : S,CNHC ou sur chaque azote : S,CNHC,S. Leurs précurseurs ont pu être synthétisés dans des conditions « ecofriend », novatrices et permettant une grande variabilité. Ces ligands offrent une grande variété de modes de coordination qui s’est traduit dans leurs complexes de coordination d’argent(I) et de palladium(II). Le potentiel catalytique de ces composés a été évalué en réaction de couplage croisé de Suzuki-Miyaura, et a révélé une très bonne activité vis-à-vis des substrats bromés
The objective of this thesis was the developement of new polyfunctional ligands families to study, in a first time, their coordination chemistry towards metallic centers, and in a second time, in view of the nature of the species formed their physical and/or catalytic properties. The combination of donor sites which seems the most interesting was based on the association of donors known to form strong interactions with the metals envisaged, like phosphines (P-) or N-heterocyclic carbenes (CNHC-), with more labile donors, like a thioether function (S-). This association allows the formation of systems called “hemilabiles”, which showed good candidates for homogenous catalytic applications. Ligands of type: diaminophosphine/thioether: P-, P-, S- have been developed. These ligands showed various coordination modes, from which a large variety of organometallic complexes were obtained. The second target ligands were of type: N-heterocyclique carbenes (NHC), bearing a thioether group on one nitrogen atom from the cycle: S,CNHC or on both nitrogen: S,CNHC,S. Their precursors have been prepared in “ecofriend” conditions and allowing a large variability. The ligands offer also various coordination modes illustrated by their silver(I) and palladium(II) complexes. The catalytic potential of these compounds has been evaluated in the Suzuki- Miyaura cross-coupling reaction and revealed a very good activity towards brominated substrates

During this work, we have synthesised and completely characterised four new ligands, twenty two novel coordination complexes and thirteen new hybrid Metal- Organic Framework (supramolecular and coordination polymers) silver(I), Zinc(II) and copper(II)-containing with fascinating and intriguing structural architectures. To achieve these results under mild conditions, we have chosen three secondary building units or building blocks (SBU): cationic unit by the trinuclear copper [Cu3(μ3-OH)(μ- C3H3N2)3]2+, neutral complexes such as [M2(O2CC10H6CO2)].nH2O and [M3(C9H3O6)2]n.nH2O (where M = Cu(II), Zn(II), C9H3O6 3- = trianion of benzene tricarboxylic acid), O2CC10H6CO2 2- = dianionic naphthalene dicarboxylate) and finally the simple building unit, Zn(HCOO)2.2H2O. Their reactivity towards rigid or flexible "spacers" or "linker" such as 4,4 '-bipyridine (bpy), 1,2-bis(4-pyridyl)ethane has been investigated. After the literature overview, we have focussed our attention to the polyfunctional reactivity of the copper trinuclear triangular [Cu3(μ3-OH)(μ-C3H3N2)3]2+ cores. The reaction in methanol of copper trinuclear core [Cu3(C3H3N2)3(OH)(C3H4N2)2R2] ( with R = HCOO- or H3CCOO-) with 4,4'-bipyridine, trans-(1,2-bis(pyridin-4-yl))ethene and bis(pyridin-4-yl))ethane had generated five novel hybrid Metal-Organic Framework (MOFs) well characterised by single-crystal Xray diffraction, elemental analysis, InfraRed spectroscopy and Thermogravimetry Analysis (TGA). Using the 4,4'-bipyridine, the two iso-strutural MOFs 2-1 and 2-6 having intriguing structures, are isolated and crystallised in space group Ibam with a = 35.201(6) a'…, b = 13.843(2) a'…, c = 23.590(6) a'…, α = β= γ= 90°, Z = 4 for MOFs 2-1 and a = 36.098(3) a'…, b = 12.766(10) a'…, c = 24.031(2) a'…, α = β= γ= 90°, Z = 4 for MOF 2-6 . Their structure determination reveals that they have 3D supramolecular network based on the stacking of the interpenetrating 2D honeycomb layers also resulting from the self-assembly of the 22-membered macrocycles or monomeric copper hexanuclear cores. Replacing the 4,4'-bipyridine by the flexible and more longer connector trans-(1,2-bis(pyridin-4-yl))ethene in the slightly modify conditions had gave rise to the two supramolecular isomers MOF 2-2 and 2-3 which crystallise respectively in triclinic space group P1 and monoclinic space group P21/n with a = 14.3105(5) a'…, b = 15.3253(5) a'…, c = 16.4073(6) a'…, α = 99.7450(10)°, β = 108.313(2)°, γ = 98.198(2)°, Z = 1 (for MOF 2-2) and a = 24.9689(8) a'…, b = 17.2737(5) a'…, c = 29.6605(9) a'…, α = γ = 90°, β = 92.623(2)°, Z = 8 (for MOF 2-3). The rhombic grid 2D-MOF 2-2 was constructed with the self-organisation of the 26-membered macrocyles forming the monomeric unit through the strong intermolecular hydrogen bonds. This open network which exhibits various types of cavities is completely different to the polymeric 1D zigzag chain of the isomer MOF 2-3. When the 4,4'-bipyridine was replaced by the bis(pyridin-4-yl))ethane, flexible spacer with the same coordination sites , another 3D open framework, MOF 2-4 (triclinic space group P1, a = 12.5276(6) a'…, b = 13.6797(6) a'…, c = 15.5767(7) a'…, α= 92.059(2)°, β= 103.1640(10)°, γ = 92.201(2)°, Z = 2) was obtained. The polymeric crystal structure of this MOF or supramolecular coordination polymer was forming by the coordination of the branched bidimensional monomeric structure through one bis(pyridin-4-yl))ethane and the intermolecular hydrogen bonds. In these five MOF structures, there are Ï€-Ï€ interactions. These results indicate that the nature of the co-ligand or connector plays the critical role in the construction of these novel hybrid coordination polymers or Metal-Organic Frameworks. The second part of this report, described the synthesis of the new ligands and their reactivity towards metal ions of Group 11 and 12. In fact, these N-donors chelating and bridging ligands named (bis(indazol-1-yl)methane , Monoclinic with space group C2, a = 23.6048(7) a'…, b = 4.10040(10) a'…, c = 13.9516(4) a'…, α = 90°, β = 117.8300(10)° , γ = 90° , Z = 4; bis(indazol-2-yl)methane, Monoclinic with space group P21, a = 4.5053(3) a'…, b = 11.5398(8) a'…, c = 11.9930(8) a'…, α = 90°, β= 99.550(2)°, γ = 90°, Z = 2; 1-((indazol-2-yl)methyl)-indazole, Monoclinic with space group P21/c , a = 10.0876(5) a'…, b = 8.1834(4) a'…, c = 14.7602(7) a'…, α = 90°, β = 98.168(2)°, γ = 90°, Z = 4), and bis(4,5,6,7-tetrahydroindazol-1-yl)methane, orthorhombic with a space group Pccn, a = 19.1237(15) a'…, b = 8.4206(7) a'…, c = 8.4529(7) a'…, α = 90°, β = 90°, γ = 90°, Z = 4) have been synthesised using two methods: the reported well-known ''Phase Transfer Catalyst (PTC)'' and a new one here reported. The complementary confirmation of their structural characterisation was obtained from DFT calculations. By using these ligands, we have prepared and structurally characterised nine derivatives from their reaction with simple salts of d10 metals (silver(I), zinc(II), mercury(II) and Cadmium(II)). With the silver(I) salt, complex salts exhibiting the common tetracoordination on Ag(I), (3-10) [Ag(Bindm)2](NO3): monoclinic, space group P21/c, a = 11.3092(6) a'…, b = 12.2646(6) a'…, c = 20.1430(10) a'…, α= 90°, β= 98.080(2)°, γ = 90°, Z = 4 and (3-20) [Ag(Bitim)2](NO3): triclinic, space group P1, a = 9.1219(9) a'…, b = 14.2797(13) a'…, c = 24.510(3) a'…, α = 79.043(4)°, β= 79.298(3)°, γ = 77.068(3)°, Z = 4 containing two moieties Bindm or Bitim are reported. Also reported is a neutral derivative containing two ligands Bindm, showing the interesting six-coordination on Cd(II) (3-17) [CdCl2(Bindm)2]: triclinic, space group P1, a = 7.9331(12) a'…, b= 7.9480(12) a'…, c = 12.5068(18) a'…, α = 83.519(7)°, β = 72.527(7)°, γ = 67.587(6)° and Z= 1. With the mercury and zinc salts, it was observed that only one ligand molecule is chelating the metal centre which is then occupies the center of distorted tetrahedral. It is the case of the following five reported derivatives (3-21) [ZnCl2(Bitim)] (triclinic space group P1, a = 7.3686(18) a'…, b = 9.388(2) a'…, c = 12.975(3) a'…, α = 80.438(6)°, β= 74.252(6)°, γ = 86.260(7)°, Z = 2); (3-6) [ZnBr2(Bindm)] (Orthorhombic, space group Pnma, a = 13.2080(11) a'…, b = 14.2483(12) a'…, c = 8.5448(7) a'…, α= 90°, β= 90°, γ = 90°, Z = 4); (3-5) [ZnCl2(Bindm)](monoclinic, space group P21/m, a = 7.2900(11) a'…, b = 14.101(2) a'…, c = 8.2929(13) a'…, α= 90°, β= 112.802(4)°, γ = 90°, Z = 2); (3-11) [Hg(SCN)2(Bindm)](monoclinic, space group P21/n, a = 12.3387(5) a'…, b = 8.1098(3) a'…, c = 18.1621(7) a'…, α = 90°, β = 96.9590(10)°, γ = 90°, Z = 4) and (3-13) [HgCl2(Bindm)](triclinic, space group P1, a = 11.7136(5) a'…, b = 12.5791(5) a'…, c = 14.1761(6) a'…, α = 72.102(2)°, β= 71.534(2)°, γ = 79.366(2)°, Z = 2). Analogously to the work carried out in chapter 2, variety of diamine linkers (en, tn, pn, bipy, bipyetha, bipyethe) and/or monodentate N-donor ligand (pyrazole, imidazole and some of their derivatives) have been reacted at room temperature with a series of metal acceptors Zn(OOCH)2.2H2O, Zn(O2C-naph-CO2)2.3H2O or Zn(NDC)2.3H2O, Zn3(1,3,5-BTC)2.8H2O, CuNDC. 3H2O and Cu3(1,2,3-BTC)2.3H2O (where 1,3,5-BTC3- = 1,3,5-benzenetricarboxylate trianion, 1,2,3-BTC3- = 1,2,3-benzenetricarboxylate trianion and NDC2- = naphthalene dicarboxylate dianion) to obtain twenty nine new derivatives characterised by the elemental analysis, spectroscopic and X-ray diffraction techniques for someone. The reaction with zinc carboxylates have yielded the isolation of seventeen derivates among which five are completely structurally characterised: the complex derivative [Zn(imH)6](OOCH)2 (4-1), the coordination polymers 1D-MOFs (4-4){[Zn2(µ-OOCH)(OOCH)3(bipy)2(H2O)2].H2O}. and (4-7){[Zn2(OOCH)4(µ-bipyetha)].4H2O}. with a zig-zag array crystal structure; and finally, two inorganic supramolecular isomers, 1D-MOF [Zn2(OOCH)4(µ-bipyethe)]. (4-5)and 3D-MOF [Zn2(µ-OOCH)4(µ-bipyethe)(OH2)2]. (4-6). Their crystallographic parameters are the following: (4-1): Space group P21/a, a: 8.355 a'…, b: 16.9590a'… , c: 8.9400 a'…, α: 90°, β: 91.68°, γ : 90 ° ; (4-4): Orthorhombic with space group Pbca, a = 6.7651(8) a'…, b = 17.4876(19) a'…, c = 23.180(3) a'…, α = β = γ = 90°, Z = 8; (4-5): Monoclinic, P2/n, a = 8.8105(3) a'…, b = 4.8235(2) a'…, c = 16.4502(7) a'… , α= 90°, β= 102.9150(10)°, γ = 90° Z= 2; (4-6): Monoclinic, C2/c, a = 37.8876(14) a'…, b = 7.6025(3) a'…, c = 25.4422(9) a'…, α= 90°, β= 90.489(2)°, γ = 90° , Z = 8 and (4-7): Monoclinic, C2/c , a = 18.0718(9) a'…, b = 4.6178(3) a'…, c = 17.3126(9) a'…, α= 90°, β= 96.329(2)°, γ = 90°, Z = 4. We have equally isolated variety of copper(II) derivatives from which three were structurally characterised: the complex salt derivative [Cu(tn)2(H2O)2](NDC).3H2O (4- 26) which crystallises in system triclinic and Space group P1, a = 7.3274(2) a'…, b = 9.9798(3) a'…, c = 11.5687(3) a'…, α= 100.6210(10)°, β = 95.1010(10)°, γ= 97.6160(10)°, Z = 1; and two Metal-Organic Frameworks 1D {[Cu(NDC)(tn)(H2O)(µ-H2O)].1/2H2O}8 (4-25) crystallising in Monoclinic system and space group P21/c, a = 11.4293(4) a'…, b = 10.4074(4) a'…, c = 12.4403(5) a'…, α= 90°, β= 117.2450(10)°, γ = 90°, Z = 2 and 2D {[Cu3(1,2,3-BTC)2(en)3(µ-H2O)(H2O)3].3H2O}.(4-29) with a space group P-1, a =12.157(2) a'…, b=12.874(3) a'…, c=14.054(3) a'…, α= 75.08(3)°, β= 74.45(3)°, γ = 68.03(3)°. Similarly to the previous derivatives reported in chapter 2, the connector trans-(1,2-bis(pyridin-4-yl))ethene (bipyethe) reacted with zinc formate (simple unit) concomitantly gave rise to two supramolecular isomers. The MOFs (base either on zinc carboxylate or copper carboxylate derivatives) exhibit in the overall crystal structures various types of open cavities or channels with someone occupy with solvent or water molecules. The thermal analysis show that these MOFs could be considered as perspective materials for gas storage until to 180°C. During the last part of this work, devoted to the synthesis of new coordination compounds based on phosphorous donor (mono- or di-) and N-donor ligands, we have reported the preparation of twenty one new compounds where eleven are structurally and completely characterised. In more details, seven silver adducts (either monomeric or polymeric species) were structurally characterised from the interaction of silver(I)diethyldithiocarbamate (Ag(dtc)) with phosphorous donor (mono- or di-) ligands: monomeric species (5-7)[Ag(dtc)(PMePh2)2] (monoclinic with P21/c, a =10.2830(8)a'… , b = 30.099(2)a'… , c = 10.8760(8)a'…, β =115.990(2)°, Z = 4), (5-13) [Ag(dtc)(dppet)] (monoclinic with P21/n, a = 9.9615(9)a'… , b =17.923(2)a'… , c =16.932(2)a'…, β = 95.235(2)°, Z = 4); dimeric species (5-1) [Ag(dtc)(PPh3)]2 ( triclinic, space group P1, a=10.410(1)a'…, b = 10.641(1)a'…, c = 10.867(1)a'…, α = 92.523(3)°, β = 93.573(3)°, γ = 109.409(3)°, Z = 1 dimer ), (5-3) [Ag(dtc)(P-m-tolyl3)] (triclinic with space group P1, a = 10.373(1) a'…, b = 11.441(1) a'…, c = 12.275(2) a'…, α = 71.407(2)° , β = 68.949(2)°, γ = 84.512(2)°, Z = 1 dimer ), (5-8) [Ag(dtc)(dppm)]2 (monoclinic with space group C21/c , a = 24.022(6)a'…, b = 10.234(2)a'… , c = 27.114(4)a'…, β = 118.37(2)°, Z = 4 dimers), and polymeric species or 1D polymer (5-6) [Ag(dtc)(PMePh2)]. (monoclinic with P21/n, a = 13.041(1)a'… , b = 7.4238(6)a'… , c = 19.892(2)a'…, β = 93.237(2)°, Z = 4), (5-10) [Ag(dtc)(dppp)]. (monoclinic with P21/c, a = 14.880(2)a'… , b = 12.035(2)a'… , c = 18.025(2)a'…, β = 101.09(1)°, Z = 4). Apart from derivative (5-1) where Silver (I) is pentacoordinated (P2AgS3), all the derivatives exhibit the tetracoordination (P2AgS2 or PAgS3) on silver centre. By reacting variety simple salts of Cu(I) with the 2,9-dimethyl-1,10- phenanthroline (dmp), eight new copper (I) derivatives have isolated among which, four were structurally characterized: (5-14) [Cu(dmp)(MeCN)]NO3 (monoclinic with P21/c, a = 10.8080(4)a'… , b = 19.5740(8)a'… , c = 7.8400(3)a'…, β = 111.206(1)°), (5-15) [Cu(dmp)2]NO3 (monoclinic with C2/c, a = 17.648(4)a'… , b =11.698(2)a'… , c = 12.466(3)a'…, β = 113.61(3)°), (5-16) [Cu(dmp)2]ClO4 ( ), (5-17) [Cu(dmp)2]Cl (triclinic with space group P1, a = 12.799(3)a'… , b = 13.598(3)a'… , c = 18.688(4)a'…, α = 70.011(3)° , β = 80.498(3)°, γ = 64.332(3)°).

Les synthèses de ligands chélatés P,N ainsi que celles de leurs complexes de métaux de transition ont suscité un intéret croissant durant ces dernières années, du fait de leurs propriétés struturales intrinsèques et du large champs d’applications. De tels ligands hétérofonctionnels associants un donneur dur, l’azote, et un donneur mou, le phosphore, peuvent conduire à une grande diversité de propriétés chimiques et structurales, et peuvent également générer des systèmes hémilabiles plus réactifs. Nous nous sommes particulièrement intéressé aux systèmes phosphines-thiazoline et phosphines-oxazoline, qui sont souvent actifs en catalyse d’oligomérisation d’olefine. Nous nous sommes également intéressé aux complexes du Pt(II) à ligands fonctionnels tel que PPh2CH2PPh2 (dppm), qui montrent d’intéressantes propriétés de luminescence
The synthesis of P,N chelating ligands and their transition metals complexes has become increasingly attractive in the last few years owing to their intrinsic structural properties and broad applications. Such heterofunctional ligands possess a hard nitrogen donor with a soft phosphorus donor leading to considerable chemical and structural diversity and may generate hemilabile systems endowed with enhanced reactivity. 1k, 1m We are particularly interested in thiazoline- and oxazoline-based phosphine systems, which are often active in catalytic ethylene oligomerisation. We are also interested in Pt(II) complexes derived from P,P functional ligands derived from Ph2PCH2PPh2 (dppm), which exhibit interesting luminescence properties

La préparation de briques élémentaires de pillar[5]arènes « clickables » nous ont permis de construire des édifices moléculaires complexes, en greffant différents groupements fonctionnels autour du coeur macrocyclique. Dans ce contexte, des nouveaux dérivés du pillar[5]arène présentant des propriétés cristaux-liquides ont été synthétisés en greffant du p-dodecyloxybenzoate ou encore des dendrons de type percec. D’autres part, des dérivés pillarèniques portant des unités de porphyrines ont été préparés à partir du squelette « clickable » pillar[5]arène et de porphyrines de Zinc portant des fonctions alcynes vrai. Les études de ce système par RMN du proton à des températures variables ont permis de mettre en évidence un équilibre conformationnel dynamique conduisant au repliement des molécules. Ceci a été expliqué par une complexation intramoléculaire des porphyrines de Zinc par les groupements 1,2,3-triazole. Finalement un support « clickable » detype [2]rotaxane comportant une porphyrine base libre comme bouchon, a été préparé et ensuite fonctionnalisé par dix porphyrines de Zinc permettant l’obtention d’un dispositif supramoléculaire photoactif
Clickable pillar[5]arene building blocks have been used for the efficient grafting of peripheral subunits onto the macrocyclic core. New liquid-crystalline pillar[5]arene derivatives have been prepared by grafting either p-dodecyloxybenzoate groups or percec-type dendrons on the macrocyclic scaffold. On the other hand, pillar[5]arene derivatives bearing peripheral porphyrin subunits have been efficiently prepared from the clickable pillar[5]arene building block and Zn(II)-porphyrin derivatives bearing a terminal alkyne function. Owing to an intramolecular complexation of the peripheral Zn(II)-porphyrin moieties by 1,2,3-triazole subunits, an original dynamic conformational equilibrium leading to a folding of the molecules has been evidenced by variable temperature 1H NMR studies. Finally, a clickable [2]rotaxane scaffold incorporating a free-base porphyrin stopper has been prepared and functionalized with ten peripheral Zn(II)-porphyrin moieties to afford a sophisticated photoactive supramolecular device

Le travail présenté dans ce manuscrit concerne la conception et les études magnéto-structurales de nouveaux systèmes de Fe(II) à transition de spin (TS), en particulier ceux faisant intervenir les tétraazamacrocycles fonctionnalisés et les ligands de type 4-R-1,2,4-triazole. L’objectif principal est l’étude de l’effet de substitution ou de solvants (ou mélange de solvants) sur le comportement élastique de ces matériaux originaux. Dans un premier temps, nous avons étudié l’effet de solvant et contre-ions sur les propriétés de commutation, dans une série des complexes [Fe(L2)](X).nH2O (L2 = 1,8-bis(2’-pyridylméthyl)-1,4,8,11-tétraaza-cyclotétradécane, X = 2(tcm)- = 2[C(CN)3]-, n = 2 (1) ; X = [Ni(CN)4]2-, n = 1 (2) ; X = (BF4)-, n = 1 (3)). Cette étude a clairement élucidé l’effet crucial des interactions hydrogène, à travers les contre-ions et les molécules de solvants, sur la coopérativité observée dans la série des trois sels. Dans un second temps, l’utilisation des ligands de type 4-R-1,2,4-triazole nous a permis l’étude de deux systèmes commutables : (i) le premier concerne un complexe trinucléaire de formule [Fe3(furmetrz)6(tcnsme)6] (furmetrz = 4-(furan-2-ylmethyl)-1,2,4-triazole ; (tcnsme)- = 1,1,3,3-tétracyano-2- thiométhylpropenure), pour lequel les études magnétiques ont mis en évidence une transition thermique en deux étapes et un effet LIESST avec une T(LIESST) de 58 K. La comparaison de ce dérivé à d’autres systèmes similaires, mais présentant une transition de spin en une seule étape, révèle que la présence de deux étapes est favorisée par de fortes interactions le long de l’axe du trimère ; (ii) le second système concerne l’étude de plusieurs séries de matériaux polyfonctionnels exhibant la transition de spin et la photoluminescence. Le résultat le plus marquant concerne la synthèse et l’étude du complexe mononucléaire [Fe(naphtrz)6](tcnsme)2.4CH3CN (naphtrz = N-(1,2,4-triazol-4-yl)-1,8-naphthalimide) pour lequel les études magnétiques et optiques ont montré l’existence des deux propriétés, d’une manière synergétique. Ce résultat prouve la possibilité de contrôler, sans ambiguïté, les propriétés optiques par des excitations extérieures telles que la température, la pression, la lumière, … Au-delà de l’aspect fondamental, ce travail ouvre aussi des perspectives très originales pour l’utilisation de ces matériaux comme capteurs ou étalons de température
This work is dedicated to the design and magnetostructural studies of new Fe(II) spin crossover (SCO) systems, in particular those involving the functionalized macrocycle and the 4-R-1,2,4-triazole triazole ligands.The principal objective concerns the study of the substitution and solvent effects on the SCO characteristics. In the first step, we have studied the solvent and the counter-ion effects, on the SCO behavior, in the series [Fe(L2)](X).nH2O (L2 = 1,8-bis(2’-pyridylméthyl)-1,4,8,11-tétraaza-cyclotétradécane, X = 2(tcm)- = 2[C(CN)3]-, n = 2 (1) ; X = [Ni(CN)4]2-, n = 1 (2) ; X = (BF4)-, n = 1 (3)), based on the macrocycles ligands. We have clearly shown in this study that the strong cooperative effects are mediated by the water solvent molecules and the counter-ions involved in the hydrogen bonding in the crystal packing. In the second step, the use of the 4-R-1,2,4-triazole fuctionalized triazole ligands led us to two original switchable systems: (i) the first one concerns the trinnuclear complex of formulae Fe3(furmetrz)6(tcnsme)6] (furmetrz = 4-(furan-2-ylmethyl)-1,2,4-triazole; (tcnsme)- = 1,1,3,3-tetracyano-2- thiométhylpropenide), for which the magnetic study reveals a two-step SCO transition and a LIESST effects with a T(LIESST) of 58 K. Examination of the intermolecular interactions in this complex and other parent trinuclear systems exhibiting complete one-step spin transition, revealed that the presence of the two-step behavior is clearly favored by strong inter-trimer interactions along the trimer axis; (ii) the second system the design and syntheses of to several series of polyfunctional materials exhibiting SCO and luminescent behaviors. In this new way, the most significant result concerns an original discrete Fe(II) complex of formulae [Fe(naphtrz)6](tcnsme)2.4CH3CN (naphtrz = N-(1,2,4-triazol-4-yl)-1,8-naphthalimide), for which the magnetic and photoluminescent studies showed that this material exhibits synergetic SCO and luminescent behaviors. This proves the possibility to control the luminescent properties through simple external perturbations such as temperature, pressure, light irradiation,… In addition, beyond the fundamental aspect, this work open new innovative perspectives for the use of such original materials as sensors or standards of temperature