Organic molecules with heavy main-group elements frequently form supramolecular links to electron-rich centres. One particular case of such interactions is halogen bonding. Most studies of this phenomenon have been concerned with either dimers or infinitely extended structures (polymers and lattices) but well-defined cyclic structures remain elusive. Here we present oligomeric aggregates of heterocycles that are linked by chalcogen-centered interactions and behave as genuine macrocyclic species. The molecules of 3-methyl-5-phenyl-1,2-tellurazole 2-oxide assemble a variety of supramolecular aggregates that includes cyclic tetramers and hexamers, as well as a helical polymer. In all these aggregates, the building blocks are connected by Te…O–N bridges. Nuclear magnetic resonance spectroscopic experiments demonstrate that the two types of annular aggregates are persistent in solution. These self-assembled structures form coordination complexes with transition-metal ions, act as fullerene receptors and host small molecules in a crystal.

Next-generation photonics envisions circuitry-free, rapidly reconfigurable systems powered by solitonic beams of self-trapped light and their particlelike interactions. Progress, however, has been limited by the need for reversibly responsive materials that host such nonlinear optical waves. We find that repeatedly switchable self-trapped visible laser beams, which exhibit strong pairwise interactions, can be generated in a photoresponsive hydrogel. Through comprehensive experiments and simulations, we show that the unique nonlinear conditions arise when photoisomerization of spiropyran substituents in pH-responsive poly(acrylamide-co-acrylic acid) hydrogel transduces optical energy into mechanical deformation of the 3D cross-linked hydrogel matrix. A Gaussian beam self-traps when localized isomerization-induced contraction of the hydrogel and expulsion of water generates a transient waveguide, which entraps the optical field and suppresses divergence. The waveguide is erased and reformed within seconds when the optical field is sequentially removed and reintroduced, allowing the self-trapped beam to be rapidly and repeatedly switched on and off at remarkably low powers in the milliwatt regime. Furthermore, this opto-chemo-mechanical transduction of energy mediated by the 3D cross-linked hydrogel network facilitates pairwise interactions between self-trapped beams both in the short range where there is significant overlap of their optical fields, and even in the long range––over separation distances of up to 10 times the beam width––where such overlap is negligible.

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Nonlinear optics and polymer systems are distinct fields that have been studied for decades. These two fields intersect with the observation of nonlinear wave propagation in photoreactive polymer systems. This has led to studies on the nonlinear dynamics of transmitted light in polymer media, particularly for optical self-trapping and optical modulation instability. The irreversibility of polymerization leads to permanent capture of nonlinear optical patterns in the polymer structure, which is a new synthetic route to complex structured soft materials. Over time more intricate polymer systems are employed, whereby nonlinear optical dynamics can couple to nonlinear chemical dynamics, opening opportunities for self-organization. This paper discusses the work to date on nonlinear optical pattern formation processes in polymers. A brief overview of nonlinear optical phenomenon is provided to set the stage for understanding their effects. We review the accomplishments of the field on studying nonlinear waveform propagation in photopolymerizable systems, then discuss our most recent progress in coupling nonlinear optical pattern formation to polymer blends and phase separation. To this end, perspectives on future directions and areas of sustained inquiry are provided. This review highlights the significant opportunity in exploiting nonlinear optical pattern formation in soft matter for the discovery of new light-directed and light-stimulated materials phenomenon, and in turn, soft matter provides a platform by which new nonlinear optical phenomenon may be discovered.

A Gaussian, visible laser beam traveling in a hydrogel doped with NaI and Ru(bpy)3Cl2 spontaneously transforms into a localized, self-trapped beam, which propagates without diverging through the medium. The catalytic, laser-light-induced oxidation of I(-) by [Ru(bpy)3](2+) generates I3(-) species, which create a refractive index increase along the beam path. The result is a cylindrical waveguide, which traps the optical field as bound modes and suppresses natural diffraction. When the beam is switched off, diffusion of I3(-) erases the waveguide within minutes and the system reverts to its original composition, enabling regeneration of the self-trapped beam. Our findings demonstrate reversible self-trapping for the first time in a precisely controllable, molecular-level photoreaction and could open routes to circuitry-free photonics devices powered by the interactions of switchable self-trapped beams.