A Matter of Fidelity: Self‐Sorting Behavior of Di‐Gold Metallotweezers

Abstract

Cation-induced high selective self-sorting is observed for reactions involving as eries of di-gold metallotweezers. The variation of the nature of the arms of the tweezers (benzo-imidazolylidene or pyrene-imidazolylidene), or the rigid bis-alkynyl linker (anthracenyl-bis-alkynyl or xanthenyl-bis-alkynyl), induces different type of selfsorting events upon addition of am etal cation (Cu + ,T l + , or Ag + ). Combining two tweezers with the same arms and different linkers produces narcissistic self-sorting.T he combination of tweezers with the same linker andd ifferent ligandsatt he arms produces social self-sorting.Biomolecules feature high selective functions in their chemical structurest hat encode their recognition or discrimination properties. Their highd egree of selectivity is guided by an accurate combination of weak interactions, and this is used by Nature to build complexb iomacromoleculara ssemblies. One of the mosti mportant properties of biomolecules is their ability to efficiently distinguish between self and nonself within complex mixtures, ap roperty knowna ss elf-sorting. [1] The selfsorting phenomenon refers to the abilityo fm ixtures of molecules to recognize their mutual counterpartss electively,s o that specific pairs are formed at the expense of ar andomm ixture of products. [2] Designing artificial self-sorting systemsi s very challenging becausem any useful materials consist of several building blocks that can interacti navarietyo fw ays. Controlling the assembly of these different buildingb locks is the key ford irecting the order and spatiald istribution of self-assembly in multicomponents upramolecular systems. [3] Producing the directed fabrication of separate ordered assemblies from mixtures of two or more assembling species with similar molecular structures is fundamental for underpinningt he productiono fn ew useful functional materials. The self-sorting phenomenon can be classified into two categories. Self-recognition (also knowna s"narcissistic" self-sorting), refers to an in- [a] Dr.

N-Heterocyclic Carbenes: A Door Open to Supramolecular Organometallic Chemistry

“…Once we studied the self-aggregation properties of tweezers 7 and 8, we became interested in studying the cation-triggered aggregates. 23 As depicted in Scheme 8, the reactions of Scheme 6. Self-Aggregation of 7 in Benzene and in the Presence of Ag + As can be seen from the description of the properties of 7 and 244 8, it became evident that their supramolecular properties are 245 determined by their tendency to self-aggregate.…”

“…The 235 reactions between the homocomplex dimers containing thallium 236 or silver also evolved to the related mixed-ligand hetero-237 complexes 9, thus indicating that 9 is the thermodynamically 238 (rather than kinetically) favored species. The formation of 9 was 239 assumed to be a consequence of the maximization of the π−π-240 stacking and metallophilic interactions in the aggregated 241 structures 23. Other examples of self-sorting phenomena shown…”

The New Di-Gold Metallotweezer Based on an Alkynylpyridine System

“…During the last few years, we reported a series of metallotweezers based on the use of two pyrene-bis-imidazolylidene-gold(I) arms bound with four different bis-alkynyl spacers (Scheme 1) [9][10][11][12][13][14][15]. These tweezers benefit from the tendency of Au(I) complexes to show linear geometry, and from the ability of the pyrene moieties to establish π-π-stacking interactions.…”

Shape‐Adaptability and Redox‐Switching Properties of a Di‐Gold Metallotweezer

“…In particular, the anthracenyl‐linked complex 1 showed a great tendency to self‐aggregate in non‐polar solvents and in the presence of cations such as Cu + , Ag + and Tl + [9] . The xanthenyl‐linked complex 2 showed interesting coordinating abilities that were highly dependent on the type of metal used [9b,10] . Finally, the carbazolyl‐linked complex 3 , was able to encapsulate planar polycyclic aromatic hydrocarbons (PAHs), displaying larger associating constants for those planar guests functionalized with groups able to hydrogen bond with the NH group of the carbazolyl spacer [11] .…”

“…[9] The xanthenyl‐linked complex 2 showed interesting coordinating abilities that were highly dependent on the type of metal used. [ 9b , 10 ] Finally, the carbazolyl‐linked complex 3 , was able to encapsulate planar polycyclic aromatic hydrocarbons (PAHs), displaying larger associating constants for those planar guests functionalized with groups able to hydrogen bond with the NH group of the carbazolyl spacer. [11] Noteworthy, all our host‐guest chemistry studies with 3 were performed using electron‐donor planar guests, thus the association constants that we found were rather low.…”