New hybrid metal-organic materials polyfunctional containing N-donor ligands

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)°).