Search

The addition of a lateral alkyl chain is a well-known strategy to reduce π-stacked ensembles of molecules in solution, with the intention to minimize the interactions between the molecules’ backbones. In this paper, we study whether this concept generalizes to single-molecule junctions by using a combination of mechanically controllable break junction (MCBJ) measurements and clustering-based data analysis with two small series of model compounds decorated with various bulky groups. The systematic study suggests that introducing alkyl side chains also favors the formation of electrode-molecule configurations that are not observed in their absence, thereby inducing broadening of the conductance peak in the one-dimensional histograms. Thus, the introduction of alkyl chains in aromatic compounds for molecular electronics must be carefully designed and optimized for the specific purpose, balancing between increased solubility and the possibility of additional junction configurations.

To date, only a small number of chemistries and chemical fueling strategies have been successfully used to operate artificial molecular motors. Here, we report the 360° directionally biased rotation of phenyl groups about a C–C bond, driven by a stepwise Appel reaction sequence. The motor molecule consists of a biaryl-embedded phosphine oxide and phenol, in which full rotation around the biaryl bond is blocked by the P–O oxygen atom on the rotor being too bulky to pass the oxygen atom on the stator. Treatment with SOCl2forms a cyclic oxyphosphonium salt (removing the oxygen atom of the phosphine oxide), temporarily linking the rotor with the stator. Conformational exchange via ring flipping then allows the rotor and stator to twist back and forth past the previous limit of rotation. Subsequently, the ring opening of the tethered intermediate with a chiral alcohol occurs preferentially through a nucleophilic attack on one face. Thus, the original phosphine oxide is reformed with net directional rotation about the biaryl bond over the course of the two-step reaction sequence. Each repetition of SOCl2–chiral alcohol additions generates another directionally biased rotation. Using the same reaction sequence on a derivative of the motor molecule that forms atropisomers rather than fully rotating 360° results in enantioenrichment, suggesting that, on average, the motor molecule rotates in the “wrong” direction once every three fueling cycles. The interconversion of phosphine oxides and cyclic oxyphosphonium groups to form temporary tethers that enable a rotational barrier to be overcome directionally adds to the strategies available for generating chemically fueled kinetic asymmetry in molecular systems.

Porphyrin cyclophane 1, consisting of two rigidly fixed but still movable cofacial porphyrins and exposing acetate-masked thiols in opposed directions of the macrocycle, is designed, synthesized, and characterized. The functional cyclophane 1, as pioneer of mechanosensitive 3D materials, forms stable single-molecule junctions in a mechanically controlled break-junction setup. Its reliable integration in a single-molecule junction is a fundamental prerequisite to explore the potential of these structures as mechanically triggered functional units and devices.

The bowl-shaped, 3-fold interlinked porphyrin dimer 2was obtained in respectable yields during macrocyclization attempts. Its bicyclic structure, consisting of a macrocycle made of a pair of acetylene interlinked tetraphenylporphyrins which are additionally linked by a C–C bond interlinking two pyrrole subunits, has been confirmed spectroscopically (2D-NMR, UV/vis, HR-MALDI-ToF MS). Late-stage functionalization provided the structural analogue 1with acetyl-protected terminal thiol anchor groups enabling single molecule transport investigations in a mechanically controlled break junction experiment. The formation of single-molecule junctions was observed, displaying large variations in the observed conductance values pointing at a rich diversity in the molecular junctions.

Matter-wave interference experiments provide a direct confirmation of the quantum superposition principle, a hallmark of quantum theory, and thereby constrain possible modifications to quantum mechanics1. By increasing the mass of the interfering particles and the macroscopicity of the superposition2, more stringent bounds can be placed on modified quantum theories such as objective collapse models3. Here, we report interference of a molecular library of functionalized oligoporphyrins4with masses beyond 25,000 Da and consisting of up to 2,000 atoms, by far the heaviest objects shown to exhibit matter-wave interference to date. We demonstrate quantum superposition of these massive particles by measuring interference fringes in a new 2-m-long Talbot–Lau interferometer that permits access to a wide range of particle masses with a large variety of internal states. The molecules in our study have de Broglie wavelengths down to 53 fm, five orders of magnitude smaller than the diameter of the molecules themselves. Our results show excellent agreement with quantum theory and cannot be explained classically. The interference fringes reach more than 90% of the expected visibility and the resulting macroscopicity value of 14.1 represents an order of magnitude increase over previous experiments2.