Based on rotational dynamics measurements carried out with isomorphic co-crystals formed by halogen-bonding (XB) between tritylacetylene halides (TrX) and diazabicyclo[2.2.2]octane (dabco), we were able to distinguish the sources of the enthalpic and entropic components in the rotational free energy barrier. We describe the formation of the 1:1 co-crystals (TrX···N(R)N) obtained from 1 equiv of dabco and 1 equiv of either TrI or TrBr, respectively, to give 4a and 4b instead of the potential 2:1 complexes. The co-crystals were prepared by solvent evaporation and mechanochemical synthesis. No co-crystal with TrCl was obtained, reflecting the weaker nature of the TrCl···NR interaction. Single-crystal X-ray diffraction confirmed structures that resemble a spinning top on a tripod and revealed that the two XB co-crystals are isomorphous, with slightly different C-X···NR (X = I, Br) distances and packing interactions. Quadrupolar-echo H NMR experiments withH-labeled samples showed that fast rotation of dabco in these co-crystals follows a six-fold potential energy surface with three lowest energy minima. Variable-temperature H NMR spin-lattice relaxation (VTH T) data revealed rotational dynamics with indistinguishable pre-exponential factors and small but distinguishable activation energies. The activation energy of 4b (E = 0.71 kcal mol) is the lowest reported in the field of amphidynamic crystals. Using the Eyring equation, we established that their activation entropy for rotation is small but negative (ΔS = -3.0 cal mol K), while there is almost a 2-fold difference in activation enthalpies, with 4a having a higher barrier (ΔH = 0.95 kcal mol) than 4b (ΔH = 0.54 kcal mol). Analysis of the rotator cavity in the two co-crystals revealed subtle differences in steric interactions that account for their different activation energies.

A modular molecular kit for the preparation of crystalline molecular rotors was devised from a set of stators and rotators to gain simple access to a large number of structures with different dynamic performance and physical properties. In this work, we have accomplished this with crystalline molecular rotors self-assembled by halogen bonding of diazabicyclo[2.2.2]octane, acting as a rotator, and a set of five fluorine-substituted iodobenzenes that take the role of the stator. Using variable-temperature (1)H T1 spin-lattice relaxation measurements, we have shown that all structures display ultrafast Brownian rotation with activation energies of 2.4-4.9 kcal/mol and pre-exponential factors of the order of (1-9) × 10(12) s(-1). Line shape analysis of quadrupolar echo (2)H NMR measurements in selected examples indicated rotational trajectories consistent with the 3-fold or 6-fold symmetric potential of the rotator.

The synthesis of conjugated Möbius molecules remains elusive since twisted and macrocyclic structures are low-entropy species sporting their own synthetic challenges. Here we report the synthesis of a Möbius macrocycle in 84% yield via alkyne metathesis of 2,13-bis­(propynyl)[5]­helicene. MALDI-MS, NMR spectroscopy, and X-ray diffraction indicated a trimeric product of twofold symmetry with PPM/MMP configurations in the helicene subunits. Alternatively, a threefold-symmetric PPP/MMM structure was determined by DFT calculations to be more thermodynamically stable, illustrating remarkable kinetic selectivity for this alkyne metathesis cyclooligomerization. Computational studies provided insight into the kinetic selectivity, demonstrating a difference of 15.4 kcal/mol between the activation barriers for the PPM/MMP and PPP/MMM diastereodetermining steps. Computational (ACID and EDDB) and experimental (UV–vis and fluorescence spectroscopy and cyclic voltammetry) studies revealed weak conjugation between the alkyne and adjacent helicene groups as well as the lack of significant global aromaticity. Separation of the PPM and MMP enantiomers was achieved via chiral HPLC at the analytical scale.

The synthesis, crystallization, single crystal X-ray structure, and solid state dynamics of molecular rotor 3 provided with a high symmetry order and relatively cylindrical bicyclo[2.2.2]octane (BCO) rotator linked to mestranol fragments were investigated in this work. Using solid state 13C NMR, three rotating fragments were identified within the molecule: the BCO, the C19 methoxy and the C18 methyl groups. To determine the dynamics of the BCO group in crystals of 3 by variable temperature 1H spin-lattice relaxation (VT 1H–T1), we determined the 1H–T1 contributions from the methoxy group C19 by carrying out measurements with the methoxy-deuterated isotopologue rotor 3-d6. The contributions from the quaternary methyl group C18 were estimated by considering the differences between the VT 1H–T1 of mestranol 8 and methoxy-deuterated mestranol 8-d3. From these studies it was determined that the BCO rotator in 3 has an activation energy of only 1.15 kcal mol−1, with a barrier for site exchange that is smaller than those of methyl (Ea = 1.35 kcal mol−1) and methoxy groups (Ea = 1.91 kcal mol−1), despite their smaller moments of inertia and surface areas.

A molecular rotor built with a stator formed by two rigid 9β-mestranol units having a 90° bent angle linked to a central phenylene rotator has an ideal structure to examine aromatic CH/π interactions. Energies and populations of the multiple solution conformations from quantum-mechanical calculations and molecular dynamics simulations were combined with variable-temperature (VT) (1)H NMR data to establish the enthalpy of this interaction and the entropy associated with rotation about a single bond. Rotational dynamics in the solid state were determined via VT cross-polarization magic-angle spinning (13)C NMR spectroscopy.

Herein we report the synthesis of the highly stable crystalline carbazole-based rotor 3 with simultaneous rapid solid state internal rotation and good fluorescence emission. Single crystal and powder X-ray diffraction studies along with microscopy revealed a phase transition from a labile benzene solvate (phase I) to highly stable crystals (phase II) that feature fast intramolecular rotation in the megahertz regime at room temperature, according to variable temperature 2 H solid state NMR experiments using isotopically enriched analogues. In addition to the megahertz rotation within its crystals, this crystal phase II displays enhanced solid state fluorescence with a higher quantum yield of ϕ = 0.28, relative to the emission of this compound in THF solution (ϕ = 0.06). These two solid state properties are significantly different from shorter compounds 1 and 2 (static and nonemissive) included here for comparison purposes.

Crystals of molecular rotor 1 with a central 1,4phenylene rotator linked to two molecules of the steroid mestranol were prepared with 1%, 5%, 20%, and up to 40% of the analogous 2, which contains a larger 2,3-difluorophenylene rotator and effectively acts as a monkey wrench that affects the rotation of the host. The packing motif of the desired P3 2 crystal form consists of 1D columns of nested rotors arranged in helical arrays with the central aromatic rotators disordered over two sites related by 85°rotation about their 1,4-axes. Rotational dynamics measured by quadrupolar echo 2 H NMR line shape analysis were analyzed in terms of a process model that involves degenerate 180°jumps in the fast exchange regime combined with a highly correlated and entropically demanding jump of 85°b etween the two dynamically disordered sites. While the enthalpic and entropic barriers for the 180°jump estimated from 2 H T 1 measurements were ΔH ⧧ = 2.7 ± 0.1 kcal mol −1 and ΔS ⧧ = −5.0 ± 0.5 cal mol −1 K −1 , respectively, the corresponding parameters for the slower 85°jumps, determined by line shape analysis, were ΔH ⧧ = 2.2 kcal mol −1 and ΔS ⧧ = −23 cal mol −1 K −1 . Increasing amounts of the larger molecular rotor 2 in the solid solution results in significant dynamic perturbations as the guest, acting as a monkey wrench, reaches values of one out of every five molecular rotors in the chain.

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