Lone-Pair-p Bond Strength Unveiled by a Combined Experimental and Computational Study.

A series of naphthalene-diimide (NDI) and perylene-diimide (PDI) connected bis-N-heterocyclic carbene complexes of iridium (III) have been prepared and fully characterized. The analysis of their NMR spectroscopic features, together their molecular structures show that these species display lone pair-p interactions between the chloride ligands of the Ir(III) complex and the heterocycles of the NDI/PDI moieties. The detection of this type of interaction in solution is due to the formation of two atropisomers, which are formed as a result of the restricted rotation about the Ir-Ccarbene bond imposed by the (Cl)lp…p interaction. Variable temperature 1H NMR analysis allowed to determine the strength of this non-covalent interaction, which lies between DH = 6.6-10 kcal/mol. The computational studies performed fully support the experimental findings. Our study demonstrates that this type of lp…p interaction is comparable to strong hydrogen bonding.

A Deeper Insight into the Supramolecular Activation of Oxidative Addition Reactions Involving Pincer-Rhodium(I) Complexes.

The factors governing the acceleration of the oxidative addition of methyl iodide to pincer rhodium(I)-complexes induced by coronene have been computationally explored in detail using quantum chemical methods. Both the parent reaction and the coronene-mediated process proceed via a stepwise SN2-type mechanism. It is found that the acceleration of the process derives from the formation of an initial supramolecular complex, mainly stabilized by electrostatic and π-π interactions, which significantly increases the electron richness of the complex. The impact of this effect on the reaction barrier has been quantitatively analyzed by applying the activation strain model in combination with the energy decomposition analysis method. In addition, the influence of other polycyclic aromatic hydrocarbons on the oxidative reaction has been also considered.

Guest-Shuttling in a Nanosized Metallobox.

An iridium-conjoined long and narrow metallorectangle was obtained by combining a quinoxalinophenanthrophenazine-connected Janus-di-imidazolylidene ligand and pyrazine. The size and shape of this assembly together with the fused polyaromatic nature of its panels provides it with properties that are uncommon for other metallosupramolecular assemblies. For example, this nanosized 'slit-like' metallobox is able show very large binding affinities with planar organic molecules in such a way, that the cavity is asymmetrically occupied by the guest molecule. This unsymmetrical conformation leads to the existence of a large amplitude motion of these guests, which slide between the two sides of the cavity of the host, thus constituting rare examples of molecular shuttles.

Tuning the Catalytic Activity of a Pincer Complex of Rhodium(I) by Supramolecular and Redox Stimuli.

We report the rhodium(I) complex [Rh(CNC-NDI)(CO)]+ , in which CNC-NDI refers to a pincer-CNC ligand decorated with a naphthalenediimide moiety. Due to the presence of the planar CNC ligand and the naphthalenediimide moiety, the electronic nature of the complex can be modulated by means of supramolecular and redox stimuli, respectively. The metal complex shows a strong π-π-stacking interaction with coronene. This interaction has an impact on the electron-richness of the metal, as demonstrated by the shifting of the ν(CO) stretching band to a lower frequency. The addition of tetrabutylammonium fluoride facilitates the sequential one- and two-electron reduction of the NDI moiety of the ligand, thus resulting in a situation in which the ligand can increase its electron-donor strength in two levels. The nature of the interaction with the fluoride anion was studied computationally. The catalytic activity of the [Rh(CNC-NDI)(CO)]+ complex was tested in the cycloisomerization of alkynoic acids, where it is observed that the activity of the catalyst can be modulated between four levels of activity, which correspond to i) the use of the unmodified catalyst, ii) catalyst+coronene, iii) catalyst+2 equivalents of fluoride, and iv) catalyst+5 equivalents of fluoride.

Supramolecular Control of the Oxidative Addition as a Way To Improve the Catalytic Efficiency of Pincer-Rhodium (I) Complexes.

1 H NMR studies using a cationic complex with a pyridine-di-imidazolylidene pincer ligand of formula [Rh(CNC)(CO)]+ revealed that this compound showed high binding affinity with coronene in CH2 Cl2 . The interaction between coronene and the planar RhI complex is established by means of π-stacking interactions. This interaction has a strong impact on the electron-donating strength of the pincer CNC ligand, which is increased significantly, as demonstrated by the shifting of the ν(CO) stretching bands to lower frequencies. The addition of coronene increases the reaction rate of the nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, and also has a positive effect on the performance of the complex as a catalyst in the cycloisomerization of 4-pentynoic acid. These findings highlight the importance of supramolecular interactions for tuning the reactivity and catalytic activity of square-planar metal complexes.

Unlocking a (Pseudo)-Mechanically Interlocked Molecule with a Coronene "Shoehorn".

Mechanically interlocked molecules (MIMs) have gained increasing interest during the last decades, not only because of their aesthetic appeal, but also because their unique properties have allowed them to find applications in nanotechnology, catalysis, chemosensing and biomedicine. Herein we describe how a pyrene molecule with four octynyl substituents can be easily encapsulated within the cavity of a tetragold(I) rectangle-like metallobox, by template formation of the metallo-assembly in the presence of the guest. The resulting assembly behaves as a mechanically interlocked molecule (MIM), in which the four long limbs of the guest protrude from the entrances of the metallobox, thus locking the guest inside the cavity of the metallobox. The new assembly resembles a metallo-suit[4]ane, given the number of protruding long limbs and the presence of the metal atoms in the host molecule. However, unlike normal MIMs, this molecule can release the tetra-substituted pyrene guest by the addition of coronene, which can smoothly replace the guest in the cavity of the metallobox. Combined experimental and computational studies allowed the role of the coronene molecule in facilitating the release of the tetrasubstituted pyrene guest to be explained, through a process that we named "shoehorning", as the coronene compresses the flexible limbs of the guest so that it can reduce its size to slide in and out the metallobox.

"Lock and Key" and "Induced-Fit" Host-Guest Models in Two Digold(I)-Based Metallotweezers.

Two different metallotweezers, each with two pyrene-imidazolylidene-gold(I) arms, were used as hosts for a series of planar aromatic guests. The metallotweezer with a dibenzoacridinebis(alkynyl) spacer (1) orients the two pyrene-imidazolylidene-gold(I) arms in a parallel disposition, with an interpanel distance of about 7 Å. The second metallotweezer (2) contains a carbazolylbis(alkynyl) spacer that directs the two pyrene panels in a diverging orientation. Determination of the association constants via 1H NMR titrations demonstrates that the binding strength shown by 1 is significantly larger than that found by 2, with binding affinities as large as 104 M-1 (in CDCl3), for the encapsulation of N,N'-dimethylnaphthalenetetracarboxydiimide with 1. The differences in the binding affinities are due to binding models associated with formation of the related host-guest complexes. While 1 operates via a "lock and key" model, in which the host does not suffer distortions upon formation of the inclusion complex, 2 operates via a guest-induced fit model. The large association constants shown by 1 with two planar guests were used for promotion of the template-directed synthesis of 1, which in the absence of an external template is produced in an equimolecular mixture with its self-aggregated congener, clippane [12]. This observation strongly suggests that the mechanically interlocked clippane is formed through a self-template-directed mechanism, while bonds are broken/formed during the synthetic protocol.

A redox-switchable catalyst with an 'unplugged' redox tag.

Two bis-(propyl-imidazolium)-napthalenediimide (NDI) salts were prepared and used as N-heterocyclic carbene (NHC) precursors for the preparation of dimetallic complexes of rhodium and iridium. Infrared spectroelectrochemical studies indicate that the metals are sensitive to changes in the electronic state of the NDI moiety. The catalytic behavior of the rhodium and iridium complexes was tested in the cycloisomerization of alkynoic acids, where the complexes showed effective redox-switching properties.

Single-Walled Carbon Nanotubes Encapsulated within Metallacycles.

Mechanically interlocked derivatives of carbon nanotubes (MINTs) are interesting nanotube products since they show high stability without altering the carbon nanotube structure. So far, MINTs have been synthesized using ring-closing metathesis, disulfide exchange reaction, H-bonding or direct threading with macrocycles. Here, we describe the encapsulation of single-walled carbon nanotubes within a palladium-based metallosquare. The formation of MINTs was confirmed by a variety of techniques, including high-resolution transmission electron microscopy. We find the making of these MINTs is remarkably sensitive to structural variations of the metallo-assemblies. When a metallosquare with a cavity of appropriate shape and size is used, the formation of the MINT proceeds successfully by both templated clipping and direct threading. Our studies also show indications on how supramolecular coordination complexes can help expand the potential applications of MINTs.

Redox-Switchable Complexes Based on Nanographene-NHCs.

A series of rhodium and iridium complexes with a N-heterocyclic carbene (NHC) ligand decorated with a perylene-diimide-pyrene moiety are described. Electrochemical studies reveal that the complexes can undergo two successive one-electron reduction events, associated to the reduction of the PDI moiety attached to the NHC ligand. The reduction of the ligand produces a significant increase on its electron-donating character, as observed from the infrared spectroelectrochemical studies. The rhodium complex was tested in the [3+2] cycloaddition of diphenylcyclopropenone and methylphenylacetylene, where it displayed a redox-switchable behavior. The neutral complex showed moderate activity, which was suppressed when the catalyst was reduced.

Clippane: A Mechanically Interlocked Molecule (MIM) Based on Molecular Tweezers.

In this study we report the preparation of a new mechanically interlocked molecule formed by the self-aggregation of two metallotweezers composed by two pyrene-imidazolylidene gold(I) arms and a pyridine-centered pentacyclic bis-alkynyl linker. The mechanically interlocked nature of this molecule arises from the presence of the bulky tert-butyl groups attached to the sides of the pyrene moieties of the arms of the tweezer, which act as stoppers avoiding the dissociation of the self-aggregated metallotweezer dimer once it is formed. By combining experimental techniques, we were able to confirm the mechanically interlocked nature of this molecule in solution, in the gas phase and in the solid state. The behavior of the tert-butyl substituted tweezer differs greatly form that shown by the tweezer lacking of these bulky groups, whose dimeric structure is in equilibrium with the monomeric structure, therefore not showing any mechanical coercion that avoids the disassembly of the self-aggregated structure.

Insights into the past and future of Janus-di-N-heterocyclic carbenes.

Janus di-N-heterocyclic carbene (NHC) ligands are a subclass of poly-NHCs that feature coordination to two transition metals in a facially opposed manner. The combination of the structural features of Janus type ligands, with the properties conferred by the NHC ligands, has conferred Janus-di-NHCs with privileged attributes for their use in diverse areas of research, such as homogeneous catalysis, materials chemistry and supramolecular chemistry. In molecular chemistry, Janus di-NHCs constitute one of the most useful chemical platforms for constructing dimetallic structures, and this includes both homo- and hetero-dimetallic compounds. This review aims to cover the most relevant advances in the use of Janus-di-NHCs during the last 15 years, by classifying them according to their specific structural features.

Redox-Switchable Cycloisomerization of Alkynoic Acids with Napthalenediimide-Derived N-Heterocyclic Carbene Complexes.

Two naphthalene-diimide (NDI) bis-imidazolium salts have been used as N-heterocyclic carbene (NHC) precursors for the preparation of NDI-functionalized complexes of rhodium and iridium of general formula [MCl(NDI-NHC)(COD)] (M=Rh, Ir; NDI-NHC=NDI-functionalized NHC ligand). Comparison of the IR spectra of the complexes [IrCl(NDI-NHC)(CO)2 ] and their related one- and two-electron reduced forms, reveal that each one-electron reduction produces a decrease of the average ν(CO) of 9-10 cm-1 , indicating a significant enhancement of the electron-richness of the metal. The [MCl(NDI-NHC)(COD)] complexes were tested in the catalytic cycloisomerization of alkynoic acids. The one-electron reduced forms showed greatly enhanced activities. For the cyclization of 5-hexynoic acid, the two-electron reduction of the ligand produced further enhancement of the catalytic activity, therefore showing that the catalyst can switch between three redox species with three distinct catalytic activities.

Shape-Adaptability and Redox-Switching Properties of a Di-Gold Metallotweezer.

The use of a carbazolyl-connected di-gold(I) metallotweezer for the encapsulation of several electron-poor organic substrates, and a planar Au(III) complex containing a CNC pincer ligand, is described. The binding affinity of the receptor depends on the electron-deficient character of the planar guest, with larger association constants found for the more electron-poor guests. The X-ray diffraction molecular structures of two host:guest adducts show that the host approaches its arms in order to facilitate the optimum interaction with the surface of the planar guests, in a clear example of an guest-induced fit conformational arrangement. The electrochemical studies of the encapsulation of N,N'-dimethyl-naphthalenetetracarboxy diimide (NTCDI) show that the redox active guest is released from the receptor upon one electron reduction, thus constituting an example of redox-switchable binding.

Ion Mobility Mass Spectrometry Uncovers Guest-Induced Distortions in a Supramolecular Organometallic Metallosquare.

The encapsulation of the tetracationic palladium metallosquare with four pyrene-bis-imidazolylidene ligands [1]4+ with a series of organic molecules was studied by Electrospray ionization Travelling Wave Ion-Mobility Mass Spectrometry (ESI TWIM-MS). The method allowed to determine the Collision Cross Sections (CCSs), which were used to assess the size changes experienced by the host upon encapsulation of the guest molecules. When fullerenes were used as guests, the host is expanded ΔCCS 13 Å2 and 23 Å2 , for C60 or C70 , respectively. The metallorectangle [1]4+ was also used for the encapsulation of a series of polycyclic aromatic hydrocarbons (PAHs) and naphthalenetetracarboxylic diimide (NTCDI), to form complexes of formula [(NTCDI)2 (PAH)@1]4+ . For these host:guest adducts, the ESI IM-MS studies revealed that [1]4+ is expanded by 47-49 Å2 .. The energy-minimized structures of [1]4+ , [C60 @1]4+ , [C70 @1]4+ , [(NTCDI)2 (corannulene)@1]4+ in the gas phase were obtained by DFT calculations.Introduction.

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

The field of metallosupramolecular chemistry is clearly dominated by the use of O-, N-, and P-donor Werner-type polydentate ligands. These molecular architectures are of high interest because of their wide range of applications, which include molecular encapsulation, stabilization of reactive species, supramolecular catalysis, and drug delivery, among others. Only recently, organometallic ligands have allowed the preparation of a variety of supramolecular coordination complexes, and the term supramolecular organometallic complexes (SOCs) is gaining space within the field of metallosupramolecular chemistry. While the early examples of SOCs referred to supramolecular architectures mostly containing bisalkenyl, diphenyl, or bisalkynyl linkers, the development of SOCs during the past decade has been boosted by the parallel development of multidentate N-heterocyclic carbene (NHC) ligands. The first examples of NHC-based SOCs referred to supramolecular assemblies based on polydentate NHC ligands bound to group 11 metals. However, during the last 10 years, several planar poly-NHC ligands containing extended π-conjugated systems have facilitated the formation of a large variety of architectures in which the supramolecular assemblies can contain metals other than Cu, Ag, and Au. Such ligands are Janus di-NHCs and trigonal-planar tris-NHCs-most of them prepared by our research group-which have allowed the preparation of a vast range of NHC-based metallosupramolecular compounds with interesting host-guest chemistry properties. Although the number of SOCs has increased in the past few years, their use for host-guest chemistry purposes is still in its earliest infancy. In this Account, we describe the achievements that we have made during the last 4 years toward broadening the applications of planar extended π-conjugated NHC ligands for the preparation of organometallic-based supramolecular structures, including their use as hosts for some selected organic and inorganic guests, together with the catalytic properties displayed by some selected host-guest inclusion complexes. Our contribution describes the design of several Ni-, Pd-, and Au-based metallorectangles and metalloprisms, which we used for the encapsulation of several organic substrates, such as polycyclic aromatic hydrocarbons (PAHs) and fullerenes. The large binding affinities found are ascribed to the incorporation of two cofacial panels with large π-conjugated systems, which provide the optimum conditions for guest recognition by π-π-stacking interactions. We also describe a series of digold(I) metallotweezers for the recognition of organic and inorganic substrates. These metallotweezers were used for the recognition of "naked" metal cations and polycyclic aromatic hydrocarbons. The recognition properties of these metallotweezers are highly dependent on the nature of the rigid connector and of the ancillary ligands that constitute the arms of the tweezer. A peculiar balance between the self-aggregation properties of the tweezer and its ability to encapsulate organic guests is observed.

Template-Controlled Synthesis of Polyimidazolium Salts by Multiple [2+2] Cycloaddition Reactions.

The tetrakisimidazolium salt H4 -2(Br)4 , featuring a central benzene linker and 1,2,4,5-(nBu-imidazolium-Ph-CH=CH-) substituents reacts with Ag2 O in the presence of AgBF4 to yield the tetranuclear, oktakis-NHC assembly [3](BF4 )4 . Cation [3]4+ features four pairs of olefins from the two tetrakis-NHC ligands perfectly arranged for a subsequent [2+2] cycloaddition. Irradiation of [3](BF4 )4 with a high pressure Hg lamp connects the two tetra-NHC ligands through four cyclobutane linkers to give compound [4](BF4 )4 . Removal of the template metals yields the novel oktakisimidazolium salt H8 -5(BF4 )8 . The tetrakisimidazolium salt H4 -2(BF4 )4 and the oktakisimidazolium salt H8 -5(BF4 )8 have been used as multivalent anion receptors and their anion binding properties towards six different anions have been compared.

Dimensional Matching versus Induced-Fit Distortions: Binding Affinities of Planar and Curved Polyaromatic Hydrocarbons with a Tetragold Metallorectangle.

A tetragold(I) rectangle-like metallocage containing two pyrene-bis-imidazolylidene ligands and two carbazolyl-bis-alkynyl linkers is used for the encapsulation of a series of polycyclic aromatic hydrocarbons (PAHs), including corannulene. The binding affinities obtained for the encapsulation of the planar PAHs guests in CD2 Cl2 are found to exponentially increase with the number of π-electrons of the guest (1.3 > logK >6.6). For the bowl-shaped molecule of corannulene, the association constant is much lower than the expected one according to its number of electrons. The molecular structure of the host-guest complex formed with corannulene shows that the molecule of the guest is compressed, while the host is expanded, thus showing an interesting case of artificial mutual induced-fit arrangement.

A resorcinarene-based tetrabenzoimidazolylidene complex of rhodium.

A tetrabenzoimidazolium-resorcinarene cavitand was used for the preparation of a tetra-benzoimidazolylidene of rhodium, which is unprecedented in the field of poly-NHC metal complexes. Both the experimental and computational analyses of the molecule reveal a distorted vase conformation as the most stable one, although several non-interconverting conformational isomers due to the restricted rotation about the Rh-C(carbene) bond coexist in the product. There is a fluxional behaviour involving the vase-kite interconversion. The main interactions between the arms of the cavitand are mostly concentrated on the terminal organometallic fragments attached to NHC, along with those between -CH3 and a N-heterocyclic carbene ring from benzoimidazoles.

A palladium-hinged organometallic square with a perfect-sized cavity for the encapsulation of three heteroguests.

A nanometer-sized tetrapalladium metallosquare with a pyrene-bisimidazolylidene ligand was found to display a perfect-sized cavity for the encapsulation of three heteroguests, enabling the formation of quintuple D-A-D-A-D stacks. The encapsulating properties of the metallosquare are clearly determined by the presence of the pyrene panels, which endow the metallosquare with a three-dimensional shape, and also behave as effective antennae for π-stacking interactions.