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Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry.

ABSTRACT: Cyclic tetrameric complexes have been prepared by the reaction of Pd(en)Cl2 or Pd(dapol)Cl2, or their nitrato analogues, with Na2(5'GMP) in aqueous solution, where en=1,2-diaminoethane, dapol=1,3-diamino-2-propanol, and 5'GMP=guanosine 5'-monophosphate. Addition of certain small molecules containing hydrophobic groups resulted in the expansion of the tetramer to a cyclic hexamer with strong bonding of one guest per hexameric host. At pH 5-6, the guest molecule can be a cation, anion, or neutral, and those species containing trimetylsilyl and t-butyl groups bonded the most strongly. The size of the central cavity of the [Pd(en)(5'GMP)]6 host has been estimated to be 5.2 A. Formation of the host-guest complex caused a large upfield shift (Deltadelta) of 2.5-2.9 ppm in the 1H NMR spectrum of the most highly affected guest protons, which were those in closest proximity to the guanine nucleobases. NOESY spectra were used to determine the interaction sites between the host and the guest. Apparent association constants determined at 26 degrees C and pD 5.4 for the [Pd(en)(5'GMP)]6-DSS and [Pd(en)(5'GMP)]6-t-butanol systems, where DSS is 3-(trimethylsilyl)-1-propanesulfonate anion, were 1.36+/-0.11x10(4) and 2.74+/-0.95x10(4) M(-3/2), respectively. The Pd(dapol)-5'GMP system forms hexameric host-guest complexes, similar in nature to those of the Pd(en)-5'GMP system. The molecular and crystal structures of Pd(dapol)Cl2 are also reported.

SUBMITTER: Walmsley JA

PROVIDER: S-EPMC2713930 | biostudies-literature | 2007 Nov

REPOSITORIES: biostudies-literature

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Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry.

Walmsley Judith A JA Zhu Shourong S Matilla Antonio A Donowick Tiffanee G TG Cramp Jessica E JE Tercero Jose Manuel JM Dalrymple Tatyana T

Inorganic chemistry 20071009 23

Cyclic tetrameric complexes have been prepared by the reaction of Pd(en)Cl2 or Pd(dapol)Cl2, or their nitrato analogues, with Na2(5'GMP) in aqueous solution, where en=1,2-diaminoethane, dapol=1,3-diamino-2-propanol, and 5'GMP=guanosine 5'-monophosphate. Addition of certain small molecules containing hydrophobic groups resulted in the expansion of the tetramer to a cyclic hexamer with strong bonding of one guest per hexameric host. At pH 5-6, the guest molecule can be a cation, anion, or neutral, ...[more]

PMID: 17924617

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Project description:We investigated Xe binding in a previously reported paramagnetic metal-organic tetrahedral capsule, [Co4L6]4-, where L2- = 4,4'-bis[(2-pyridinylmethylene)amino][1,1'-biphenyl]-2,2'-disulfonate. The Xe-inclusion complex, [XeCo4L6]4-, was confirmed by 1H NMR spectroscopy to be the dominant species in aqueous solution saturated with Xe gas. The measured Xe dissociation rate in [XeCo4L6]4-, koff = 4.45(5) × 102 s-1, was at least 40 times greater than that in the analogous [XeFe4L6]4- complex, highlighting the capability of metal-ligand interactions to tune the capsule size and guest permeability. The rapid exchange of 129Xe nuclei in [XeCo4L6]4- produced significant hyperpolarized 129Xe chemical exchange saturation transfer (hyper-CEST) NMR signal at 298 K, detected at a concentration of [XeCo4L6]4- as low as 100 pM, with presaturation at -89 ppm, which was referenced to solvated 129Xe in H2O. The saturation offset was highly temperature-dependent with a slope of -0.41(3) ppm/K, which is attributed to hyperfine interactions between the encapsulated 129Xe nucleus and electron spins on the four CoII centers. As such, [XeCo4L6]4- represents the first example of a paramagnetic hyper-CEST (paraHYPERCEST) sensor. Remarkably, the hyper-CEST 129Xe NMR resonance for [XeCo4L6]4- (δ = -89 ppm) was shifted 105 ppm upfield from the diamagnetic analogue [XeFe4L6]4- (δ = +16 ppm). The Xe inclusion complex was further characterized in the crystal structure of (C(NH2)3)4[Xe0.7Co4L6]·75 H2O (1). Hydrogen bonding between capsule-linker sulfonate groups and exogenous guanidinium cations, (C(NH2)3)+, stabilized capsule-capsule interactions in the solid state and also assisted in trapping a Xe atom (∼42 Å3) in the large (135 Å3) cavity of 1. Magnetic susceptibility measurements confirmed the presence of four noninteracting, magnetically anisotropic high-spin CoII centers in 1. Furthermore, [Co4L6]4- was found to be stable toward aggregation and oxidation, and the CEST performance of [XeCo4L6]4- was unaffected by biological macromolecules in H2O. These results recommend metal-organic capsules for fundamental investigations of Xe host-guest chemistry as well as applications with highly sensitive 129Xe-based sensors.

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Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry.

Publications

Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry.

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