Narcissistic Self-Sorting and Enhanced Luminescence via Catenation in Water

Narcissistic self-sorting, namely that components are able to distinguish “self” from “nonself” during self-assembly, was accomplished via catenation by condensing multiple hydrazides and an aldehyde, or a hydrazide and multiple aldehydes in water. The underneath mechanism of this behavior relies on the corresponding homo [2]catenanes are thermodynamically more favored than their hetero counterparts, because the former containing two identical macrocyclic components are able to maximize the inter-component noncovalent forces. One of these catenanes contains four 4-phenylpyridinium units, which are often considered barely luminescent due to intramolecular rotations and vibrations that lead to nonradiative annihilation of their excited states. These intramolecular motions, however, are restricted upon integrating 4-phenylpyridiniums within the catenane architecture. As a consequence, compared to its non-interlocked counterparts, this catenane exhibits enhanced fluorescence, which represents a novel conceptual model for developing luminescent materials.

Flyby reaction trajectories: Chemical dynamics under extrinsic force

Dynamic effects are an important determinant of chemical reactivity and selectivity, but the deliberate manipulation of atomic motions during a chemical transformation is not straightforward. Here, we demonstrate that extrinsic force exerted upon cyclobutanes by stretching pendant polymer chains influences product selectivity through force-imparted nonstatistical dynamic effects on the stepwise ring-opening reaction. The high product stereoselectivity is quantified by carbon-13 labeling and shown to depend on external force, reactant stereochemistry, and intermediate stability. Computational modeling and simulations show that, besides altering energy barriers, the mechanical force activates reactive intramolecular motions nonstatistically, setting up “flyby trajectories” that advance directly to product without isomerization excursions. A mechanistic model incorporating nonstatistical dynamic effects accounts for isomer-dependent mechanochemical stereoselectivity.

How Do Molecular Motions Affect Structures and Properties at Molecule and Aggregate Levels?

<p>Experimental and theoretical analysis demonstrated that the active intramolecular motions in the excited state of all molecules at single molecule level imparted them with more twisted structural conformations and weak emission. However, owing to the restriction of intramolecular motions in the nano/macro aggregate state, all the molecules assumed less twisted conformations with bright emission. Synergic strong and weak intermolecular interactions allowed their crystals to undergo reversible deformation, which effectively solved the problem of the brittles of organic crystals, meanwhile imparted them with excellent elastic performance. </p>

How Do Molecular Motions Affect Structures and Properties at Molecule and Aggregate Levels?

<p>Experimental and theoretical analysis demonstrated that the active intramolecular motions in the excited state of all molecules at single molecule level imparted them with more twisted structural conformations and weak emission. However, owing to the restriction of intramolecular motions in the nano/macro aggregate state, all the molecules assumed less twisted conformations with bright emission. Synergic strong and weak intermolecular interactions allowed their crystals to undergo reversible deformation, which effectively solved the problem of the brittles of organic crystals, meanwhile imparted them with excellent elastic performance. </p>