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Self-Assembled M?L? Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes.

ABSTRACT: Metallosupramolecular cages of the general formulas [M?(L)?][X]? can be self-assembled in good yields, where M = Pd, X = NO?, L = L¹ (1a); M = Pd, X = OTf, L = L¹ (1b); M = Pt, X = OTf, L = L¹ (2); M = Pd, X = OTf, L = L² (3); L¹ = 1,3-bis(pyridin-3-ylethynyl)-5-methoxybenzene; and L² = 2,6-(pyridin-3-ylethynyl)- 4-methoxyaniline, respectively. These cages have been fully characterized using ¹H, ¹³C NMR, elemental analysis, IR spectroscopy, and electrospray mass spectrometry. Additionally the molecular structure of [Pd?(L¹)?][OTf]? (1b) was confirmed using single crystal X-ray diffraction. The capacity of central cavities of M?L? cages to accommodate square planar metal complexes was investigated. In particular, the tetracationic cage [Pd?(L²)?][OTf]? (3) was found to encapsulate the anionic metal complex [PtCl?]^2- through electrostatic interactions and also via hydrogen bonding with the amino groups of the bridging ligand displayed by this nanocage.

SUBMITTER: Desmarets C

PROVIDER: S-EPMC5453161 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Self-Assembled M₂L₄ Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes.

Desmarets Christophe C Ducarre Thierry T Rager Marie Noelle MN Gontard Geoffrey G Amouri Hani H

Materials (Basel, Switzerland) 20140109 1

Metallosupramolecular cages of the general formulas [M₂(L)₄][X]₄ can be self-assembled in good yields, where M = Pd, X = NO₃, L = L¹ (1a); M = Pd, X = OTf, L = L¹ (1b); M = Pt, X = OTf, L = L¹ (2); M = Pd, X = OTf, L = L² (3); L¹ = 1,3-bis(pyridin-3-ylethynyl)-5-methoxybenzene; and L² = 2,6-(pyridin-3-ylethynyl)- 4-methoxyaniline, respectively. These cages have been fully characterized using ¹H, 13C NMR, elemental a ...[more]

PMID: 28788457

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Project description:The kinetics of the hydration reaction on trans-[Pt(NH3)2(pyrX)Cl]+ (pyr = pyridine) complexes (X = OH-, Cl-, F-, Br-, NO2 -, NH2, SH-, CH3, C?CH, and DMA) was studied by density functional theory calculations in the gas phase and in water solution described by the implicit polarizable continuum model method. All possible positions ortho, meta, and para of the substituent X in the pyridine ring were considered. The substitution of the pyr ligand by electron-donating X's led to the strengthening of the Pt-N1(pyrX) (Pt-NpyrX) bond and the weakening of the trans Pt-Cl or Pt-Ow bonds. The electron-withdrawing X's have exactly the opposite effect. The strengths of these bonds can be predicted from the basicity of sigma electrons on the NpyrX atom determined on the isolated pyrX ligand. As the pyrX ring was oriented perpendicularly with respect to the plane of the complex, the nature of the X···Cl electrostatic interaction was the decisive factor for the transition-state (TS) stabilization which resulted in the highest selectivity of ortho-substituted systems with respect to the reaction rate. Because of a smaller size of X's, the steric effects influenced less importantly the values of activation Gibbs energies ?G ? but caused geometry changes such as the elongation of the Pt-NpyrX bonds. Substitution in the meta position led to the highest ?G ? values for most of the X's. The changes of ?G ? because of electronic effects were the same in the gas phase and the water solvent. However, as the water solvent dampened electrostatic interactions, 2200 and 150 times differences in the reaction rate were observed between the most and the least reactive mono-substituted complexes in the gas phase and the water solvent, respectively. An additional NO2 substitution of the pyrNO2 ligand further decelerated the rate of the hydration reaction, but on the other hand, the poly-NH2 complexes were no more reactive than the fastest o-NH2 system. In the gas phase, the poly-X complexes showed the additivity of the substituent effects with respect to the Pt-ligand bond strengths and the ligand charges.

Dataset Information

Self-Assembled M?L? Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes.

Publications

Self-Assembled M₂L₄ Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes.

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