Highly oriented and polyoxometalate-incorporating surface-attached metal-organic frameworks for efficient dye adsorption and water oxidation.

We present a facile protocol for the controlled growth of highly oriented and polyoxometalate-incorporating HKUST-1 SURMOFs. Combining the spin-coating technique with alcohol-vapour induced growth, film thickness, crystallite orientation and crystal size can be precisely tuned. The SURMOFs exhibit excellent abilities in selective adsorption of cationic dyes and water oxidation.

Liquid-Phase Epitaxial Growth of Highly Oriented and Multivariate Surface-Attached Metal-Organic Frameworks.

Multivariate metal-organic frameworks (MTV-MOFs) incorporating multiple chemical functionalities within single-phase crystalline materials show superior properties that arise from synergistic effects. Herein, we report an efficient and versatile method for the growth of highly oriented multivariate surface-attached MOFs (MTV-SURMOFs) by the combination of the liquid-epitaxial growth method (LPE) and the mixed-linker strategy. Twenty-six MTV-SURMOFs of the [MLP] type with a maximum of five different dicarboxylate linkers (L) were deposited onto suitably functionalized surfaces.

Amplified cross-linking efficiency of self-assembled monolayers through targeted dissociative electron attachment for the production of carbon nanomembranes.

The determination of the negative ion yield of 2'-chloro-1,1'-biphenyl (2-Cl-BP), 2'-bromo-1,1'-biphenyl (2-Br-BP) and 2'-iodo-1,1'-biphenyl (2-I-BP) upon dissociative electron attachment (DEA) at an electron energy of 0 eV revealed cross section values that were more than ten times higher for iodide loss from 2-I-BP than for the other halogenides from the respective biphenyls (BPs). Comparison with dissociative ionization mass spectra shows that the ratio of the efficiency of electron impact ionization induced fragmentation of 2-I-BP, 2-Br-BP, and 2-Cl-BP amounts to approximately 1:0.7:0.

Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers.

Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM-ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial.

Minimization of Surface Energies and Ripening Outcompete Template Effects in the Surface Growth of Metal-Organic Frameworks.

As well-oriented, surface-bound metal-organic frameworks become the centerpiece of many new applications, a profound understanding of their growth mode becomes necessary. This work shows that the currently favored model of surface templating is in fact a special case valid only for systems with a more or less cubic crystal shape, while in less symmetric systems crystal ripening and minimization of surface energies dominate the growth process.

Transition voltages respond to synthetic reorientation of embedded dipoles in self-assembled monolayers.

We studied the influence of embedded dipole moments in self-assembled monolayers (SAMs) formed on template stripped Au surfaces with liquid eutectic Ga-In alloy as a top electrode. We designed three molecules based on a -terphenyl structure in which the central aromatic ring is either phenyl or a dipole-inducing pyrimidyl in one of two different orientations. All three form well defined SAMs with similar thickness, packing density and tilt angle, with dipole moments embedded in the SAM, isolated from either interface.