The connection of lipophilic gallic acid derivatives at the 5,5'- or 6,6'-positions of the rigid 2,6-bis(1-ethyl-benzimidazol-2-yl)pyridine core provides two pro-mesogenic tridentate ligands L10 and L12, whose molecular shapes, anisometries, and directional intermolecular pi-stacking can be tuned. X-ray diffraction data in the crystalline state, combined with solution 1H NMR measurements, show that complexation with trivalent lanthanides, Ln(III), produces the neutral hemi-disklike complexes [Ln(Li)(NO3)3] (i = 10, 12), which dimerize to give the rodlike bimetallic complexes [Ln2(Li)2(NO3)6] at lower temperature. The relevant thermodynamic parameters for the latter process depend on the nature of the ligand, the size of the metal ion, and the strength of the intermolecular interactions involved in the condensed phase. These three-dimensional models obtained for the complexes in the crystals and in solution are eventually confronted with small-angle XRD profiles recorded in the intermediate thermotropic liquid crystalline phase, in which the rigidity of the packed polyaromatic cores is maintained, while the alkyl chains are molten. According to the specific geometries and nuclearities of the molecular complexes, three types of mesophases (lamellar, columnar, and cubic) can be induced, which provides a direct correlation between the microscopic arrangements and the macroscopic ordering in lanthanide-containing metallomesogens.
Reaction of the bis-tridentate ligand bis[1-ethyl-2-[6'-(N,N-diethylcarbamoyl)pyridin-2'-yl]benzimidazol-5-yl]methane (L2) with Ln(CF(3)SO(3))(3).xH(2)O in acetonitrile (Ln = La-Lu) demonstrates the successive formation of three stable complexes [Ln(L2)(3)](3+), [Ln(2)(L2)(3)](6+), and [Ln(2)(L2)(2)](6+). Crystal-field independent NMR methods establish that the crystal structure of [Tb(2)(L2)(3)](6+) is a satisfying model for the helical structure observed in solution. This allows the qualitative and quantitative beta23 (bi,Ln1,Ln2)characterization of the heterobimetallic helicates [(Ln(1))(Ln(2))(L2)(3)](6+). A simple free energy thermodynamic model based on (i) an absolute affinity for each nine-coordinate lanthanide occupying a terminal N(6)O(3) site and (ii) a single intermetallic interaction between two adjacent metal ions in the complexes (DeltaE) successfully models the experimental macroscopic constants and allows the rational molecular programming of the extended trimetallic homologues [Ln(3)(L5)(3)](9+).
Supporting information for this article is available on the WWW under http://www.chemeurj.org/ or from the author. Table S1 lists the ESI-MS peaks, and Table S2 the 1 H NMR signals observed for mixtures of the heterotrimetallic complexes [(Ln 1) x (Ln 2) 3Àx (L9) 3 ] 9 + in acetonitrile. Tables S3 and S4 list experimental and S5 calculated mole fractions for the heterotrimetallic complexes obtained under different stoichiometric conditions. Table S6 collects structural data for the triple-helical cation in the crystal structure of [La 0.96 Eu 2.04 (L9) 3 ](CF 3 SO 3) 9 (CH 3 NO 2) 9 (1). Figures S1 and S2 show ESI-MS and 1 H NMR spectra obtained for different stoichiometric ratios Ln 1 :Ln 2 :L9. La 0.96 (L9) 3 ](CF 3 SO 3) 9 (CH 3 NO 2) 9 (1, Eu 2.04 La 0.96 C 207 H 222 N 48 O 51 S 9 F 27 , monoclinic, P2 1 /c, Z = 4) in which the cation [EuLaEu(L9) 3 ] 9 + is the major component in the crystal. The scope and limitation of this approach is discussed together with the conditions for explicitly considering intermetallic interaction parameters u Ln1Ln2 in more sophisticated chemical models.
The influence of rigid or semirigid dicarboxylate anions, terephtalate (TerP(2-)), isophtalate (IsoP(2-)), and phenylenediacetate (PDA(2-)) on the self-condensation process of the [Mo(2)O(2)S(2)](2+) dioxothio cation has been investigated. Three new molybdenum rings, [Mo(12)O(12)S(12)(OH)(12)(TerP)](2-) ([Mo(12)TerP](2-)), [Mo(16)O(16)S(16)(OH)(16)(H(2)O)(4)(PDA)(2)](4-) ([Mo(16)(PDA)(2)](4-)), and [Mo(16)O(16)S(16)(OH)(16)(H(2)O)(2)(IsoP)(2)](4-) ([Mo(16)(IsoP)(2)](4-)) have been isolated and unambiguously characterized in the solid state by single-crystal X-ray studies and in solution by various NMR methods and especially by diffusion-correlated NMR ((1)H DOSY) spectroscopy, which was shown to be a powerful tool for the characterization and speciation of templated molybdenum ring systems in solution. Characterization by FT-IR and elemental analysis are also reported. The dynamic and thermodynamic properties of both the sixteen-membered rings were studied in aqueous medium. Specific and distinct behaviors were revealed for each system. The IsoP(2-)/[Mo(2)O(2)S(2)](2+) system gave rise to equilibrium, involving mono-templated [Mo(12)IsoP](2-) and bis-templated [Mo(16)(IsoP)(2)](4-) ions. Thermodynamic parameters have been determined and showed that the driving-force for the formation of the [Mo(16)(IsoP)(2)](4-) is entropically governed. However, whatever the conditions (temperature, proportion of reactants), the PDA(2-)/[Mo(2)O(2)S(2)](2+) system led only to a single compound, the [Mo(16)(PDA)(2)](4-) ion. The latter exhibits dynamic behavior, consistent with the gliding of both the stacked aromatic groups. Stability and dynamics of both Mo(16) rings was related to weak hydrophobic or pi-pi stacking inter-template interactions and inner hydrogen-bond network occurring within the [Mo(16)(IsoP)(2)](4-) and [Mo(16)(PDA)(2)](4-) ions.
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