Adaptive Se‐Te Metathesis Controlled by Cucurbituril‐Based Host‐Guest Interaction

Abstract

Regulating the reactivity and equilibrium of a dynamic reaction is essential for adaptive chemistry and functional materials. Herein, cucurbituril‐based host‐guest interaction was embedded into the dynamic metathesis between diselenide and ditelluride to establish an equilibrium‐adaptive system. In this system, cucurbit[6]uril (CB[6]) selectively bound with diselenide while cucurbit[7]uril (CB[7]) bound with not only diselenide but also ditelluride and exchange product. The dynamic nature of diselenide bond was locked after forming the inclusion complex with CB[6]. Based on this selective locking effect, the Se−Te products were reversed back to diselenide and ditelluride reactants, which was an equilibrium regulating process. Therefore, by combining CB[6]‐based host‐guest interaction and dynamic diselenide chemistry, the reactivity of diselenide bond and the equilibrium of Se−Te metathesis was successfully regulated.

Metal-Free Supramolecular Catalytic Hydrolysis of Ammonia Borane through Cucurbituril Nanocavitands

“…Recently, Eelkema et al have established control on the catalytic activity of a copper­(I)-carbene catalyst for the alkyne–azide cycloaddition reaction through cucurbit[7]­uril (CB7) encapsulation . Cucurbit[5]­uril (CB5) (Figure ), the smallest CB homologue, has been used to bind O 2 , N 2 , and noble gases inside the cavity and cations such as NH 4 + and Pb 2+ at its carbonyl portals and also used as a capping agent to synthesize gold nanoparticles. − CB7 and CB8 show strong ion–dipole interaction through their carbonyl portals with organic fluorescent dyes/drugs/peptides and modulate their molecular properties and are beneficial for various applications. − Over the last few years, the host–guest complexes, biomacromolecular assemblies, and nanocomposites functionalized with cucurbiturils have shown potential applications in sensors, , artificial microtubules, heterogeneous electrocatalytic CO 2 reduction, controlled Se–Te metathesis, modulating biochemical reactions, , bioimaging, peptide transport, supramolecular antidotes, treatment of diabetes, and so forth. Contributing in this line to overcome the issues associated with catalytic hydrolysis of AB, we have employed the strategy of metal-free cucurbituril cavitation of AB for the first time to explore the effective catalytic hydrolysis of AB at room temperature.…”

“…28−30 CB7 and CB8 show strong ion−dipole interaction through their carbonyl portals with organic fluorescent dyes/drugs/peptides and modulate their molecular properties and are beneficial for various applications. 31−37 Over the last few years, the host−guest complexes, biomacromolecular assemblies, and nanocomposites functionalized with cucurbiturils have shown potential applications in sensors, 38,39 artificial microtubules, 40 heterogeneous electrocatalytic CO 2 reduction, 41 controlled Se−Te metathesis, 42 modulating biochemical reactions, 39,43 bioimaging, 44 peptide transport, 45 supramolecular antidotes, 46 treatment of diabetes, 47 and so forth. Contributing in this line to overcome the issues associated with catalytic hydrolysis of AB, we have employed the strategy of metal-free cucurbituril cavitation of AB for the first time to explore the effective catalytic hydrolysis of AB at room temperature.…”

Reliable prediction of association (free) energies of supramolecular complexes with heavy main group elements – the HS13L benchmark set

“…48 7 is a ditelluride (HOC3Te) 2 guest interacting via chalcogen bonding to CB [7]. 49 Complexes 8 to 13 are charged systems. 8 and 9 both have the +4 charged cyclobis-(paraquat-p-phenylene) host, which is the highest charge considered.…”

Ru–Se Coordination: A New Dynamic Bond for Visible-Light-Responsive Materials

“…While light induces cycloadditions/reversions, it can also induce isomerization, cyclization, and other side reactions. 23,24 As another type of dynamic bond, sensitized alkoxyamines, 10 hexaarylbiimidazoles, 25 disulfides, 26,27 allyl sulfides, 13,28 thiuram disulfides, 29 trithiocarbonates, 30 and other sulfides 31,32 Se), 33 selenide−sulfide (Se−S), 34 and selenide−telluride (Se− Te), 35 have been investigated. These Se-containing dynamic bonds can be excited by visible light because they exhibit lower bond energies in comparison to their sulfide analogues.…”

“…Such reactions are also induced by UV light or short-wavelength visible light. To red-shift the excitation wavelength, several dynamic bonds based on selenium (Se), such as diselenide (Se–Se), selenide–sulfide (Se–S), and selenide–telluride (Se–Te), have been investigated. These Se-containing dynamic bonds can be excited by visible light because they exhibit lower bond energies in comparison to their sulfide analogues.…”