Simultaneous Endo- and Exo-Complex Formation of Pyridine[4]arene Dimer with Neutral and Anionic Guests

The formation of complexes between hexafluorophosphate (PF6−) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI‐QTOF‐MS, IM‐MS, DFT calculations), in the solid state (X‐ray crystallography), and in chloroform solution (1H, 19F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6− anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase. peerReviewed

Ion mobility-mass spectrometry of supramolecular complexes and assemblies

Despite their structural and functional differences, synthetic supramolecular assemblies share many similarities with biological assemblies, especially enzymes. The assemblies can be on the same length scale, and their structures and guest binding are typically governed by non-covalent interactions. Thus, only relatively weak interactions define the shape of a synthetic supramolecule or the secondary and tertiary structure of a protein, such that the resulting dynamism makes structure elucidation challenging. For biomolecules such as peptides, proteins, glycans and lipids this has often been tackled using ion mobility–mass spectrometry (IM-MS), whereby analyte ions are separated according t…

Superchiral Pd 3 L 6 Coordination Complex and Its Reversible Structural Conversion into Pd 3 L 3 Cl 6 Metallocycles

Large, non-symmetrical, inherently chiral bispyridyl ligand L derived from natural ursodeoxycholic bile acid was used for square-planar coordination of tetravalent Pd(II) , yielding the cationic single enantiomer of superchiral coordination complex 1 Pd3 L6 containing 60 well-defined chiral centers in its flower-like structure. Complex 1 can readily be transformed by addition of chloride into a smaller enantiomerically pure cyclic trimer 2 Pd3 L3 Cl6 containing 30 chiral centers. This transformation is reversible and can be restored by the addition of silver cations. Furthermore, a mixture of two constitutional isomers of trimer, 2 and 2', and dimer, 3 and 3', can be obtained directly from …

Simultane endo - und exo -Komplexbildung von Pyridin[4]aren-Dimeren mit neutralen und anionischen Gästen

Reactivity of anticancer metallodrugs with serum proteins: New insights from size exclusion chromatography-ICP-MS and ESI-MS

International audience; A method based on the coupling of high resolution size-exclusion liquid chromatography using a polymer stationary phase with inductively coupled plasma mass spectrometry was developed to study the interactions of two metallodrugs - cisplatin and RAPTA-T - with the serum proteins albumin and transferrin. In contrast to previous approaches, the technique allowed the total recovery of the metals from the column and was able to discriminate between the different species of the metallodrugs and their complexes with the proteins at femtomolar detection levels. Metal binding was found to be dependent on the protein concentration and on the incubation time of the sample. Cis…

Multinuclear Cytotoxic Metallodrugs: Physicochemical Characterization and Biological Properties of Novel Heteronuclear Gold-Titanium Complexes

An unprecedented series of titanocene-gold bi- and trimetallic complexes of the general formula [[(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)](m)AuCl(x)](q+) (n = 0, 2, or 4; m = 1, x = 1, q = 0 or m = 2, x = 0, q = 1) have been prepared and characterized spectroscopically. The luminescence spectroscopy and photophysics of one of the compounds, [[(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)PPh(2))TiCl(2)](2)Au]PF(6), have been investigated in 2MeTHF solution and in the solid state at 77 and 298 K. Evidence for interfragment interactions based on the comparison of electronic band positions and emission lifetimes, namely, triplet energy transfer (ET) from the Au- to the Ti-containing…

DOSY NMR, X-ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M6L4 Coordination Cages.

A novel modular approach to electron-deficient and electron-rich M6L4 cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two C3-symmetric ligands L1 and L2 with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand L1 is more electron-deficient than the well-known 2,4,6-tri(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand L2 is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)Pt(OTf)2] or [(dppp)Pd(OTf)2] corner-complexes yields two electron-deficient (1a and 1b) and two electron-rich …

Simultaneous endo and exo  Complex Formation of Pyridine[4]arene Dimers with Neutral and Anionic Guests

The formation of complexes between hexafluorophosphate (PF6- ) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI-QTOF-MS, IM-MS, DFT calculations), in the solid state (X-ray crystallography), and in chloroform solution (1 H, 19 F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6- anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase.

CCDC 1062272: Experimental Crystal Structure Determination

Related Article: Pia Bonakdarzadeh, Filip Topić, Elina Kalenius, Sandip Bhowmik, Sota Sato, Michael Groessl, Richard Knochenmuss, Kari Rissanen|2015|Inorg.Chem.|54|6055|doi:10.1021/acs.inorgchem.5b01082

CCDC 1543476: Experimental Crystal Structure Determination

Related Article: Anniina Kiesilä, Lauri Kivijärvi, Ngong Kodiah Beyeh, Jani O. Moilanen, Michael Groessl, Tatiana Rothe, Sven Götz, Filip Topić, Kari Rissanen, Arne Lützen and Elina Kalenius|2017|Angew.Chem.,Int.Ed.|56|10942|doi:10.1002/anie.201704054

CCDC 1062271: Experimental Crystal Structure Determination

Related Article: Pia Bonakdarzadeh, Filip Topić, Elina Kalenius, Sandip Bhowmik, Sota Sato, Michael Groessl, Richard Knochenmuss, Kari Rissanen|2015|Inorg.Chem.|54|6055|doi:10.1021/acs.inorgchem.5b01082

CCDC 1062270: Experimental Crystal Structure Determination

Related Article: Pia Bonakdarzadeh, Filip Topić, Elina Kalenius, Sandip Bhowmik, Sota Sato, Michael Groessl, Richard Knochenmuss, Kari Rissanen|2015|Inorg.Chem.|54|6055|doi:10.1021/acs.inorgchem.5b01082