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Herein, we investigate supramolecular gelation behavior of a dendronized triphenylamine bis-urea macrocycle (1) in toluene in the presence and absence of sulfoxide chain stoppers. Macrocycle 1 assembles in the sol phase through intermolecular hy-drogen bonding interactions, spontaneously transitioning into a gel state when left undisturbed at room temperature. In tolu-ene, 1 displays a critical gelation concentration of 0.066 wt%, classifying it as a super-gelator. Furthermore, it exhibits a thermoreversible gel-sol phase transition as well as thixotropic behavior. Temperature-dependent 1H NMR spectroscopy is employed to probe the sol phase assembly of 1 with the size variations at different temperatures assessed by 2D DOSY. Rheological experiments at 10 °C were used to measure gelation response to mechanical stimuli. An amplitude sweep test highlights a linear viscoelastic region. Additionally, the self-healing behavior of gel 1 was verified through a series of strain cycles, where it showed complete recovery. Addition of chain stoppers 10% versus 1 of dimethyl sulfoxide (DMSO) and diphenyl sulfoxide (DPS) lead to weaker gels with smaller differences between the storage and the loss moduli. Rheological analysis revealed slower/partial recovery for the gel containing chain stoppers. Gels assembled from macrocyclic building blocks may retain homogeneous binding cavity and channels offering novel functional properties. 

An empirical model was developed to predict organic solvophobic effects using N-phenylimide molecular balances functionalized with non-polar alkyl groups. Solution studies and X-ray crystallography confirmed intramolecular alkyl-alkyl interactions in their folded conformers. The structural modularity of the balances allowed systematic variation of alkyl group lengths. Control balances were instrumental in isolating weak organic solvophobic effects by eliminating framework solvent-solute effects. A 19F NMR label enabled analysis across 46 deuterated and non-deuterated solvent systems. Linear correlations were observed between organic solvophobic effects and solvent cohesive energy density (ced) as well as changes in solvent-accessible surface areas (SASA). Using these empirical relationships, a model was constructed to predict organic solvophobic interaction energy per unit area for any organic solvent with known CED values. The predicted interaction energies aligned with recent organic solvophobic measurements and literature values for the hydrophobic effect on non-polar surfaces confirmed the model's accuracy and utility. 

Abstract Benzylic and allylic electrophiles are well known to react faster in S_N2 reactions than aliphatic electrophiles, but the origins of this enhanced reactivity are still being debated. Galabov, Wu, and Allen recently proposed that electrostatic interactions in the transition state between the nucleophile (Nu) and the sp²carbon (C2) adjacent to the electrophilic carbon (C1) play a key role. To test this secondary electrostatic hypothesis, molecular rotors were designed that form similar through‐space electrostatic interactions with C2 in their bond rotation transition states without forming bonds to C1. This largely eliminates the alternative explanation of stabilizing conjugation effects between C1 and C2 in the transition state. The rotor barriers were strongly correlated with the experimentally measured S_N2 free energy. Notably, rotors where C2 was sp²or sp‐hybridized had barriers that were consistently 0.5–2.0 kcal mol⁻¹lower than those for rotors where C2 was sp³‐hybridized. Computational studies of atomic charges were consistent with the formation of stabilizing secondary electrostatic interactions. Further confirmation came from observing the benzylic effect in rotors where the first atom was varied, including oxygen, sulfur, nitrogen, and sp²‐carbon. In summary, these studies provided strong experimental support for the role of secondary electrostatic interactions in the S_N2 reaction. 

Abstract A new empirical electrophilicity reactivity parameter,E_RB, was developed based on the rotational barriers of a series ofN‐phenylimide molecular rotors containing various electrophilic groups. In the bond rotation transition state, these electrophilic groups form close contact with an electronegative C═O oxygen. Thus, strong electrophilic groups significantly lowered the rotational barrier. As a result, the rotational barriers were inversely correlated with the strengths of the electrophiles. The rotational barriers were measured by dynamic NMR (EXSY), enabling the quantification across a wide range of types of electrophiles. Computational analysis confirmed that the observed variations arose from intramolecular interactions in the transition state, where the C═O oxygen served as a probe of both the electrophilic group's electrostatic potential and steric accessibility. By simultaneously capturing attractive and repulsive transition state interactions,E_RBprovides an effective means of predicting electrophilicity and reactivity trends across a broad range of electrophiles and reaction types. The utility ofE_RBwas initially validated using a series of rotors containing Michael addition electrophiles, followed by broader application to a diverse array of reactions involvingsp³andsp²electrophiles, including S_N2, S_NAr, Pd‐oxidative addition, and Sonogashira reactions. 

The ability to control molecular-scale motion using electrostatic interactions was demonstrated using an N -phenylsuccinimide molecular rotor with an electrostatic pyridyl-gate. Protonation of the pyridal-gate forms stabilizing electrostatic interactions in the transition state of the bond rotation process that lowers the rotational barrier and increases the rate of rotation by two orders of magnitude. Molecular modeling and energy decomposition analysis confirm the dominant role of attractive electrostatic interactions in lowering the bond rotation transition state. 

Abstract Cooperative behavior and orthogonal responses of two classes of coordinatively integrated photochromic molecules towards distinct external stimuli were demonstrated on the first example of a photo‐thermo‐responsive hierarchical platform. Synergetic and orthogonal responses to temperature and excitation wavelength are achieved by confining the stimuli‐responsive moieties within a metal–organic framework (MOF), leading to the preparation of a novel photo‐thermo‐responsive spiropyran‐diarylethene based material. Synergistic behavior of two photoswitches enables the study of stimuli‐responsive resonance energy transfer as well as control of the photoinduced charge transfer processes, milestones required to advance optoelectronics development. Spectroscopic studies in combination with theoretical modeling revealed a nonlinear effect on the material electronic structure arising from the coordinative integration of photoresponsive molecules with distinct photoisomerization mechanisms. Thus, the reported work covers multivariable facets of not only fundamental aspects of photoswitch cooperativity, but also provides a pathway to modulate photophysics and electronics of multidimensional functional materials exhibiting thermo‐photochromism.