Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion

Molecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom-up layer-by-layer assembly of oriented overcrowded-alkene molecular motors forming a crystalline metal–organic framework thin film. While all stator parts of the overcrowded-alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light-induced molecular rotation. Taking advantage of the thin film\u27s transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta-)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials

Photoresponsive porous materials

Molecular machines, switches, and motors enable control over nanoscale molecular motion with unprecedented precision in artificial systems. Integration of these compounds into robust material scaffolds, in particular nanostructured solids, is a fabrication strategy for smart materials with unique properties that can be controlled with external stimuli. Here, we describe a subclass of these structures, namely light-responsive porous materials metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), and porous aromatic frameworks (PAFs) appended with molecular photoswitches. In this review, we provide an overview of a broad range of light-responsive porous materials focusing on potential applications

Visible-Light-Driven Tunable Molecular Motors Based on Oxindole

Molecular rotary motors based on oxindole which can be driven by visible light are presented. This novel class of motors can be easily synthesized via a Knoevenagel condensation, and the choice of different upper halves allows for the facile tuning of their rotational speed. The four-step rotational cycle was explored using DFT calculations, and the expected photochemical and thermal isomerization behavior was confirmed by NMR, UV/vis, and CD spectroscopy. These oxindole motors offer attractive prospects for functional materials responsive to light

A chiral self-sorting photoresponsive coordination cage based on overcrowded alkenes

In recent years, increasing efforts have been devoted to designing new functional stimuli-responsive supramolecular assemblies. Here, we present three isomeric supramolecular coordination complexes consisting of a Pd2L4 stoichiometry. As shown by NMR, CD and X-ray studies, as well as DFT calculations, these complexes form cage-like structures by chiral self-sorting. Photochromic ligands derived from first generation molecular motors enable light-driven interconversion between the three isomers. Two of the isomers were able to form host–guest complexes opening up new prospects toward stimuli-controlled substrate binding and release.Supramolecular & Biomaterials Chemistr

Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge- Transport

Despite their ubiquity, self-assembled monolayers (SAMs) of thiols on coinage metals are difficult to study and are still not completely understood, particularly with respect to the nature of thiol-metal bonding. Recent advances in molecular electronics have highlighted this deficiency due to the sensitivity of tunneling charge-transport to the subtle differences in the overall composition of SAMs and the chemistry of their attachment to surfaces. These advances have also challenged assumptions about the spontaneous formation of covalent thiol-metal bonds. This paper describes a series of experiments that correlate changes in the physical properties of SAMs to photoelectron spectroscopy to unambiguously assign binding energies of noncovalent interactions to physisorbed disulfides. These disulfides can be converted to covalent metal-thiolate bonds by exposure to free thiols, leading to the remarkable observation of the total loss and recovery of length-dependent tunneling charge-transport. The identification and assignment of physisorbed disulfides solve a long-standing mystery and reveal new, dynamic properties in SAMs of thiols

Visible-Light-Driven Rotation of Molecular Motors in a Dual-Function Metal-Organic Framework Enabled by Energy Transfer

The visible-light-driven rotation of an overcrowded alkene-based molecular motor strut in a dual-function metal-organic framework (MOF) is reported. Two types of functional linkers, a palladium-porphyrin photosensitizer and a bispyridine-derived molecular motor, were used to construct the framework capable of harvesting low-energy green light to power the rotary motion. The molecular motor was introduced in the framework using the postsynthetic solvent-assisted linker exchange (SALE) method, and the structure of the material was confirmed by powder (PXRD) and single-crystal X-ray (SC-XRD) diffraction. The large decrease in the phosphorescence lifetime and intensity of the porphyrin in the MOFs upon introduction of the molecular motor pillars confirms efficient triplet-to-triplet energy transfer between the porphyrin linkers and the molecular motor. Near-infrared Raman spectroscopy revealed that the visible light-driven rotation of the molecular motor proceeds in the solid state at rates similar to those observed in solution

Asymmetric Synthesis of Second-Generation Light-Driven Molecular Motors

The enantiomeric homogeneity of light-driven molecular motors based on overcrowded alkenes is crucial in their application as either unidirectional rotors or as chiral multistate switches. It was challenging to obtain these compounds as single enantiomers via the established synthetic procedures due to loss of optical purity in the key step, i.e., the Barton–Kellogg olefination reaction. Searching for strategies to avoid racemization, a new class of light-driven molecular motors was designed, synthesized, and studied. The stereochemical integrity was fully preserved throughout the synthesis, and on the basis of photochemical and kinetic studies using UV/vis, CD, and ¹H NMR spectroscopy, it was established that they still function properly as unidirectional molecular motors

Multistate Switching of Spin Selectivity in Electron Transport through Light-Driven Molecular Motors

It is established that electron transmission through chiral molecules depends on the electron's spin. This phenomenon, termed the chiral‐induced spin selectivity (CISS), effect has been observed in chiral molecules, supramolecular structures, polymers, and metal‐organic films. Which spin is preferred in the transmission depends on the handedness of the system and the tunneling direction of the electrons. Molecular motors based on overcrowded alkenes show multiple inversions of helical chirality under light irradiation and thermal relaxation. The authors found here multistate switching of spin selectivity in electron transfer through first generation molecular motors based on the four accessible distinct helical configurations, measured by magnetic‐conductive atomic force microscopy. It is shown that the helical state dictates the molecular organization on the surface. The efficient spin polarization observed in the photostationary state of the right‐handed motor coupled with the modulation of spin selectivity through the controlled sequence of helical states, opens opportunities to tune spin selectivity on‐demand with high spatio‐temporal precision. An energetic analysis correlates the spin injection barrier with the extent of spin polarization

Cooperative light-induced breathing of soft porous crystals via azobenzene buckling

Although light is a prominent stimulus for smart materials, the application of photoswitches as light-responsive triggers for phase transitions of porous materials remains poorly explored. Here we incorporate an azobenzene photoswitch in the backbone of a metal-organic framework producing light-induced structural contraction of the porous network in parallel to gas adsorption. Light-stimulation enables non-invasive spatiotemporal control over the mechanical properties of the framework, which ultimately leads to pore contraction and subsequent guest release via negative gas adsorption. The complex mechanism of light-gated breathing is established by a series of in situ diffraction and spectroscopic experiments, supported by quantum mechanical and molecular dynamic simulations. Unexpectedly, this study identifies a novel light-induced deformation mechanism of constrained azobenzene photoswitches relevant to the future design of light-responsive materials

Ultrafast Excited State Dynamics in a First Generation Photomolecular Motor

Efficient photomolecular motors will be critical elements in the design and development of molecular machines. Optimisation of the quantum yield for photoisomerisation requires a detailed understanding of molecular dynamics in the excited electronic state. Here we probe the primary photophysical processes in the archetypal first generation photomolecular motor, with sub-50 fs time resolved fluorescence spectroscopy. A bimodal relaxation is observed with a 100 fs relaxation of the Franck-Condon state to populate a red-shifted state with a reduced transition moment, which then undergoes multi-exponential decay on a picosecond timescale. Oscillations due to the excitation of vibrational coherences in the S 1 state are seen to survive the ultrafast structural relaxation. The picosecond relaxation reveals a strong solvent friction effect which is thus ascribed to torsion about the C−C axle. This behaviour is contrasted with second generation photomolecular motors; the principal differences are explained by the existence of a barrier on the excited state surface in the case of the first-generation motors which is absent in the second generation. These results will help to provide a basis for designing more efficient molecular motors in the future