Photoresponsive self-assembled monolayers (SAMs) were fabricated on gold surfaces using cucurbit[7]uril (CB[7])-based host-guest complexes. In this architecture, the macrocyclic CB[7] unit serves as a universal anchoring platform, with one portal binding to the gold surface and the opposite portal encapsulating a photoswitchable molecular rod featuring a pyridinium-adamantyl recognition site. Four distinct molecular rods were synthesized to demonstrate the versatility of this modular approach. In solution, all supramolecular complexes retained the inherent photoresponsive behavior of the parent rods, exhibiting reversible isomerization with high fatigue resistance and minimal perturbation from CB[7] complexation. Upon surface immobilization, the resulting monolayers retained functional photoactivity, as demonstrated on all four systems. These results underscore the potential of CB[7]-anchored assemblies for the fabrication of robust, light-responsive surfaces and molecular devices.

Photoswitchable molecular systems confined at solid interfaces often exhibit altered photochemical behavior due to strong substrate coupling and restricted molecular motion. Here, we investigate whether a triptycene-based tripodal platform can effectively decouple photoactive units from metallic and nonmetallic surfaces in Langmuir-Blodgett (LB) films. Four structurally distinct photoswitches were incorporated into a common tripodal scaffold and assembled into organized monolayers at the air-water interface, followed by transfer onto quartz and gold substrates. Comprehensive characterization confirms the formation of homogeneous, monomolecular films with controlled thickness (∼2 nm) and reproducible surface coverage. UV-vis spectroscopy reveals that the photochemical response of surface-bound systems closely resembles that observed in solution, with comparable switching behavior and thermal kinetics on both substrates. Notably, no systematic differences are observed between metallic and nonmetallic surfaces, demonstrating effective electronic decoupling by the tripodal architecture. In contrast, the azobenzene-containing system exhibits asymmetric switching behavior governed by intermolecular packing within the monolayer, rather than substrate interactions. These findings establish tripodal molecular platforms as a robust strategy for preserving intrinsic photoswitch functionality in surface-confined environments and provide key design principles for photoswitchable interfaces.

A supramolecular complex acting as a molecular rotor was assembled from cucurbit[7]uril and a rigid, rod-shaped molecular anchor. This rotor was then anchored to the facets of a hexagonal tris(o-phenylenedioxy)cyclotriphosphazene matrix, forming a regular 2D array. Semi-empirical calculations revealed very low rotational barriers for the macrocyclic units within this array, suggesting smooth rotational motion and promising potential for future applications in dynamic molecular systems.

Two light-driven molecular motors, fused to a triptycene-based tetrapodal platform, with rotational axes oriented either parallel or perpendicular to the surface, were successfully designed and synthesized. Both systems demonstrated complete 360° rotation cycles, efficient photoswitching at 385 ± 5 nm (reaching ∼90% at the photostationary state), and quantitative thermal helix inversion with half-lives of ∼7 min at 20 °C. When assembled as monolayers on gold surfaces, the motors retained their full rotational functionality, demonstrating the ability of the tetrapodal platform to minimize surface interactions. These findings highlight the potential of these systems for applications in surface-integrated molecular devices and machines.

Dielectric spectroscopy has been used to determine the barriers of rotation of surface-mounted fullerenes (2.3 ± 0.1 and 4.3 ± 0.1 kcal mol-1). In order to achieve this, a C60 derivative equipped with an anchoring group designed to form a surface inclusion with the hexagonal form of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) has been synthesized. Solid-state NMR analysis revealed that approximately 50% of the surface-mounted molecules have a chemical environment different from the others suggesting two distinct insertion modes. These observations correlate with results of DFT calculations.

Accelerating the rotational speed of light-driven molecular motors is among the foremost concerns in molecular machine research, as this speed directly influences the performance of a motor. Controlling the motor’s rotation is crucial for practical applications, and using an oriented external electric field (OEEF) represents a feasible method to achieve this objective. We have investigated the impact of an OEEF on the optical and kinetic properties of a novel π-donor/acceptor di-substituted molecular motor, R2,3-(NH2, CHO). We employed density functional theory (DFT) and time-dependent DFT methods to analyze the electronic excitation and thermal isomerization behavior. Our results demonstrate that the absorption wavelength, absorption efficiency of the motor, and rate constant of the thermal isomerization reaction can be adjusted by applying OEEFs, which are predictable based on the dipole moment and polarizability of the molecules under consideration. In particular, we observed a shift in the absorption wavelength toward longer ranges, an enhancement in light absorption intensity, and an acceleration in the rotation rate when applying a weak positive directional external electric field to the R2,3-(NH2, CHO) motor. In summary, this theoretical study highlights the potential of OEEFs for improving the performance of molecular motors.

Molecular platforms are essential components of various surface-mounted molecular devices. Here, we document the synthesis of two universal triptycene-based tripodal pedestals featuring terminal alkynes in the axial position. We showcase their versatility by incorporating them into the structures of diverse functional molecules such as unidirectional light-driven molecular motors, photoswitches, and Brownian molecular rotors using standard cross-coupling reactions. We also present their fundamental physical properties, including acidity constants, data from differential scanning calorimetry, and crystallographic analysis of two parent and five derived structures. Finally, and importantly, we demonstrate that the photochemical properties of selected photoswitch representatives remain uncompromised when fused with tripods. Two universal triptycene-based tripodal pedestals featuring terminal alkynes in the axial position are presented. Their versatility is showcased by incorporating them into the structures of diverse functional molecules such as unidirectional light-driven molecular motors, photoswitches, and Brownian molecular rotors. image

Novel binding motifs suitable for the construction of multitopic guest-based molecular devices (e.g., switches, sensors, data storage, and catalysts) are needed in supramolecular chemistry. No rigid, aliphatic binding motif that allows for axial disubstitution has been described for cucurbit[6]uril (CB6) so far. We prepared three model guests combining spiro[3.3]heptane and bicyclo[1.1.1]pentane centerpieces with imidazolium and ammonium termini. We described their binding properties toward CB6/7 and α-/β-CD using NMR, titration calorimetry, mass spectrometry, and single-crystal X-ray diffraction. We found that a bisimidazolio spiro[3.3]heptane guest forms inclusion complexes with CB6, CB7, and β-CD with respective association constants of 4.0 × 104, 1.2 × 1012, and 1.4 × 102. Due to less hindering terminal groups, the diammonio analogue forms more stable complexes with CB6 (K = 1.4 × 106) and CB7 (K = 3.8 × 1012). The bisimidazolio bicyclo[1.1.1]pentane guest forms a highly stable complex only with CB7 with a K value of 1.1 × 1011. The high selectivity of the new binding motifs implies promising potential in the construction of multitopic supramolecular components.

Three symmetrically and three unsymmetrically substituted cibalackrot (7,14-diphenyldiindolo[3,2,1-de:3',2',1'-ij][1,5]naphthyridine-6,13-dione, 1) dyes carrying two derivatized phenyl rings have been synthesized as candidates for molecular electronics and especially for singlet fission, a process of interest for solar energy conversion. Solution measurements provided singlet and triplet excitation energies and fluorescence yields and lifetimes; conformational properties were analyzed computationally. The molecular properties are close to ideal for singlet fission. However, crystal structures, obtained by single-crystal X-ray diffraction (XRD), are rather similar to those of the polymorphs of solid 1, in which the formation of a charge-separated state followed by intersystem crossing, complemented with excimer formation, outcompetes singlet fission. Results of calculations by the approximate SIMPLE method suggest which ones among the solid derivatives are the best candidates for singlet fission, but it appears difficult to change the crystal packing in a desirable direction. We also describe the preparation of three specifically deuteriated versions of 1, expected to help sort out the mechanism of fast intersystem crossing in its charge-separated state.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Herein, we report radical chlorination of cubane-1,4-dicarboxylic acid leading preferentially to one monochlorinated cubane dicarboxylate (ca. 70%) that is accompanied by four dichlorinated derivatives (ca. 20% in total). The exact positions of the chlorine atoms have been confirmed by X-ray diffraction of the corresponding single crystals. The acidity constants of all dicarboxylic acids in water were determined by capillary electrophoresis (3.17 ± 0.04 and 4.09 ± 0.05 for monochlorinated and ca. 2.71 ± 0.05 and 3.75 ± 0.05 for dichlorinated cubanes). All chlorinated derivatives as well as the parent diacid showed high thermal stability (decomposition above 250 °C) as documented by differential scanning calorimetry. The probable reaction pathways leading to individual isomers were proposed, and the energies of individual transition states and intermediates were obtained using density functional theory calculations (B3LYP-D3BJ/6-311+G(d,p)). The relative strain energies for all newly prepared derivatives as well as for hypothetical hexahalogenated (fluorinated, chlorinated, brominated, and iodinated) derivatives of cubane-1,4-dicarboxylic acids were predicted using wavefunction theory methods. The hexafluorinated derivative was identified as the most strained compound (57.5 kcal/mol), and the relative strain decreased as the size of halogen atoms increased (23.7 for hexachloro, 16.7 for hexabromo, and 4.0 kcal/mol for the hexaiodo derivative).

We assembled photoresponsive mono- and bilayer systems with well-defined properties from rod-shaped molecules equipped with different photoswitches. Using properly chosen chromophores (diarylethene-based switch and unidirectional light-driven molecular motor), we then selectively targeted layers made of the same types of photoswitches using appropriate monochromatic light. UV-vis analysis confirmed smooth and unrestricted photoisomerization. To achieve this, we synthesized a new class of triptycene-based molecular pedestals adept at forming sturdy Langmuir-Blodgett films on a water-air interface. The films were smoothly transferred to gold and quartz surfaces. Repeated deposition afforded bilayer systems: one layer containing diarylethene-based photoswitches and the other a unidirectional light-driven molecular motor. Structural analysis of both mono- and bilayer systems revealed the molecules to be tilted with carboxylic functions pointing to the surface. At least two different polymorphs differing in monolayer thickness and tilt angle (~40° and ~60°) were identified on the gold surface.

Cucurbit[7]uril (CB[7]) encapsulates adamantyl and trimethylsilyl substituents of positively charged guests in dimethyl sulfoxide (DMSO). Unlike in water or deuterium oxide, addition of a selection of alkali and alkali-earth cations with van der Waals radii between 1.0 and 1.4 Å (Na+, K+, Ca2+, Sr2+, Ba2+ and Eu3+) to the CB[7]/guest complexes triggers their cation-mediated trimerization, a process that is very slow on the nuclear magnetic resonance (NMR) time scale. Smaller (Li+, Mg2+) or larger cations (Rb+, Cs+ or NH4+) are inert. The trimers display extensive CH-O interactions between the equatorial and pseudo-equatorial hydrogens of CB[7] and the carbonyl rim of the neighboring CB[7] unit in the trimer, and a deeply nested cation between the three interacting carbonylated CB[7] rims; a counteranion is likely perched in the shallow cavity formed by the three outer walls of CB[7] in the trimer. Remarkably, a guest must occupy the cavity of CB[7] for trimerization to take place. Using a combination of semi-empirical and density functional theory techniques in conjunction with continuum solvation models, we showed that trimerization is favored in DMSO, and not in water, because the penalty for the partial desolvation of three of the six CB[7] portals upon aggregation into a trimer is less unfavorable in DMSO compared to water.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A family of seven symmetrical molecular rods, which are sharing 4-ethynylpyridyl terminal groups and differ in the structure of the linker have been investigated. Although structurally related they show unique electrochemical behavior, which clearly correlates with their conformational flexibility. Two flexible compounds are reduced by two electrons. Their reduction yields intensive charge transfer UV-vis absorption bands and is accompanied by characteristic EPR spectra. In contrast, all conformationally rigid structures are reduced by four electrons and do not yield neither charge transfer bands nor distinct EPR signals. Simple irreversible voltammetry of all derivatives is similar to the reduction of 4-ethynylpyridine at -2.1 V. The experimental observations were supported by the extensive DFT calculations. Electrochemical techniques proved to be valuable in distinction between molecular rigidity and flexibility.

It is generally expected that a solvent has only marginal effect on the stability of a covalent bond. In this work, we present a combined computational and experimental study showing a surprising stabilization of the covalent/dative bond in Me3NBH3 complex with increasing solvent polarity. The results show that for a given complex, its stability correlates with the strength of the bond. Notably, the trends in calculated changes of binding (free) energies, observed with increasing solvent polarity, match the differences in the solvation energies (ΔEsolv) of the complex and isolated fragments. Furthermore, the studies performed on the set of the dative complexes, with different atoms involved in the bond, show a linear correlation between the changes of binding free energies and ΔEsolv. The observed data indicate that the ionic part of the combined ionic-covalent character of the bond is responsible for the stabilizing effects of solvents.

The present study has identified molecular bending as an important factor thathas a profound effect on the self-assembly of originally rod-shaped organic molecules on a(111) gold surface. This was demonstrated on three specifically designed rigid molecular rodscarrying archetypal anchoring groups (pyridyl units and thiols) on one terminus. These rodswere used to prepare corresponding self-assembled monolayers (SAMs), and a combinationof various analytical techniques revealed that originally straight molecular rods that were bentonce adsorbed on a metallic surface, acquiring a characteristic"J-shape". Extensive densityfunctional theory calculations, includingin silicoreconstruction of such SAMs on (111) gold,clearly confirmed experimental observations.