Understanding the Buoy Effect of Surface-Enriched Pt Complexes in Ionic Liquids: A Combined ARXPS and Pendant Drop Study.

Recently, we demonstrated that Pt catalyst complexes dissolved in the ionic liquid (IL) [C4 C1 Im][PF6 ] can be deliberately enriched at the IL surface by introducing perfluorinated substituents, which act like buoys dragging the metal complex towards the surface. Herein, we extend our previous angle-resolved X-ray photoelectron spectroscopy (ARXPS) studies at complex concentrations between 30 and 5 %mol down to 1 %mol and present complementary surface tension pendant drop (PD) measurements under ultraclean vacuum conditions. This combination allows for connecting the microscopic information on the IL/gas interface derived from ARXPS with the macroscopic property surface tension. The surface enrichment of the Pt complexes is found to be most pronounced at 1 %mol . It also displays a strong temperature dependence, which was not observed for 5 %mol and above, where the surface is already saturated with the complex. The surface enrichment deduced from ARXPS is also reflected by the pronounced decrease in surface tension with increasing concentration of the catalyst. We furthermore observe by ARXPS and PD a much stronger surface affinity of the buoy-complex as compared to the free ligands in solution. Our results are highly interesting for an optimum design of IL-based catalyst systems with large contact areas to the surrounding reactant/product phase, such as in supported IL phase (SILP) catalysis.

Formation and Surface Behavior of Pt and Pd Complexes with Ligand Systems Derived from Nitrile-functionalized Ionic Liquids Studied by XPS.

The front cover artwork is provided by the groups of Prof. Hans-Peter Steinrück and Prof. Peter Wasserscheid at the Friedrich-Alexander-Universität (FAU) Erlangen-Nürnberg. The image shows substitution of volatile acetonitrile ligands by a nitrile-functionalized imidazolium cation. The formed cationic complex and the counter ions exhibit a specific preferential orientation at the ionic liquid/gas interface, which can be studied by angle-resolved XPS. Read the full text of the Research Article at 10.1002/cphc.202200391.

Formation and Surface Behavior of Pt and Pd Complexes with Ligand Systems Derived from Nitrile-functionalized Ionic Liquids Studied by XPS.

We studied the formation and surface behavior of Pt(II) and Pd(II) complexes with ligand systems derived from two nitrile-functionalized ionic liquids (ILs) in solution using angle-resolved X-ray photoelectron spectroscopy (ARXPS). These ligand systems enabled a high solubility of the metal complexes in IL solution. The complexes were prepared by simple ligand substitution under vacuum conditions in defined excess of the coordinating ILs, [C3 CNC1 Im][Tf2 N] and [C1 CNC1 Pip][Tf2 N], to immediately yield solutions of the final products. The ILs differ in the cationic head group and the chain length of the functionalized substituent. Our XPS measurements on the neat ILs gave insights in the electronic properties of the coordinating substituents revealing differences in donation capability and stability of the complexes. Investigations on the composition of the outermost surface layers using ARXPS revealed no surface affinity of the nitrile-functionalized chains in the neat ILs. Solutions of the formed complexes in the nitrile ILs showed homogeneous distribution of the solute at the surface with the heterocyclic moieties preferentially orientated towards the vacuum, while the metal centers are rather located further away from the IL/vacuum interface.

Probing Surface and Interfacial Tension of Ionic Liquids in Vacuum with the Pendant Drop and Sessile Drop Method.

We report on the surface and interface tension measurements of the two ionic liquids (ILs) [C8C1Im][PF6] and [m(PEGn)2Im]I (n = 2, 4, 6) in a surface science approach. The measurements were performed in a newly developed and unique experimental setup, which allows for surface tension (ST) measurements using the pendant drop method and for contact angle measurements using the sessile drop method under the well-defined conditions of a high vacuum (from 10-7 mbar). The setup also allows for in vacuum transfer to an ultrahigh vacuum system for surface preparation and analysis, such as in angle-resolved X-ray photoelectron spectroscopy. For [C8C1Im][PF6], we observe a linear decrease in the surface tension with increasing temperature. The ST measured under high vacuum is consistently found to be larger than under ambient conditions, which is attributed to the influence of water uptake in air by the IL. For [m(PEGn)2Im]I (n = 2, 4, 6), we observe a decrease in the ST with increasing polyethylene glycol chain length in a vacuum, similar to very recent observations under 1 bar Argon. This decrease is attributed to an increasing enrichment of the PEG chains at the surface. The ST data obtained under these ultraclean conditions are essential for a fundamental understanding of the relevant parameters determining ST on the microscopic level and can serve as a benchmark for theoretical calculations, such as molecular dynamic simulations. In addition to the ST measurements, proof-of-principle data are presented for sessile drop measurements in HV, and a detailed description and characterization of the new setup is provided.

Direct Correlation of Surface Tension and Surface Composition of Ionic Liquid Mixtures-A Combined Vacuum Pendant Drop and Angle-Resolved X-ray Photoelectron Spectroscopy Study.

We investigated the surface tension and surface composition of various mixtures of the two ionic liquids (ILs) 1-methyl-3-octyl-imidazolium hexafluorophosphate [C8C1Im][PF6] and 1,3-bis(polyethylene glycol)imidazolium iodide [(mPEG2)2Im]I in the temperature range from 230 to 370 K under ultraclean vacuum conditions. The surface tension was measured using a newly developed apparatus, and the surface composition was determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). In the pure ILs, the alkyl chains of [C8C1Im][PF6] and the PEG chains of [(mPEG2)2Im]I are enriched at the IL/vacuum interface. In the mixtures, a strong selective surface enrichment of the alkyl chains occurs, which is most pronounced at low [C8C1Im][PF6] contents. For the surface tension, strong deviations from an ideal mixing behaviour take place. By applying a simple approach based on the surface composition of the mixtures as deduced from ARXPS, we are able to predict and reproduce the experimentally measured temperature-dependent surface tension values with astonishingly high accuracy.

Molecular Stacking on Graphene.

The sequential vertical polyfunctionalization of 2D addend-patterned graphene is still elusive. Here, we report a practical realization of this goal via a "molecular building blocks" approach, which is based on a combination of a lithography-assisted reductive functionalization approach and a post-functionalization step to sequentially and controllably link the molecular building blocks ethylpyridine, cis-dichlorobis(2,2'-bipyridyl)ruthenium, and triphenylphosphine (4-methylbenzenethiol, respectively) on selected lattice regions of a graphene matrix. The assembled 2D hetero-architectures are unambiguously characterized by various spectroscopic and microscopic measurements, revealing the stepwise stacking of the molecular building blocks on the graphene surface. Our method overcomes the current limitation of a one-layer-only binding to the graphene surface and opens the door for a vertical growth in the z-direction.