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.

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.

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.

The New Di-Gold Metallotweezer Based on an Alkynylpyridine System.

We developed a simple method to prepare one gold-based metallotweezer with two planar Au-pyrene-NHC arms bound by a 2,6-bis(3-ethynyl-5-tert-butylphenyl)pyridine unit. This metallotweezer is able to bind a series of polycyclic aromatic hydrocarbons through the π-stacking interactions between the polyaromatic guests and the pyrene moieties of the NHC ligands. The metallotweezer was also used as a host for the encapsulation of planar metal complexes, such as the Au(III) complex [Au(C^N^C)(C≡CC6H4-OCH3-p)], for which there is a large binding constant of 946 M-1.

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.

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.

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.

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 Matter of Fidelity: Self-Sorting Behavior of Di-Gold Metallotweezers.

Cation-induced high selective self-sorting is observed for reactions involving a series 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 self-sorting events upon addition of a metal cation (Cu+ , Tl+ , or Ag+ ). Combining two tweezers with the same arms and different linkers produces narcissistic self-sorting. The combination of tweezers with the same linker and different ligands at the arms produces social self-sorting.

A Rigid Trigonal-Prismatic Hexagold Metallocage That Behaves as a Coronene Trap.

A trigonal-prismatic hexagold cage was obtained by combining a triphenylene-tris(N-heterocyclic carbene) ligand and a carbazolyl-bis(alkynyl) linker. The metallocage has a slot-like cavity with a volume of about 300 Å3 . The cage was used for the recognition of several polycyclic aromatic hydrocarbons. Due to the perfect dimensional match, the supramolecular complex shows a very high affinity for trapping coronene.

The Complex Coordination Landscape of a Digold(I) U-Shaped Metalloligand.

A U-shaped di-gold metallotweezer with two pyrene-imidazolylidene edges and a xanthenyl-bis-alkynyl connector was prepared. This metallotweezer acts as metalloligand in the presence of Cu+ , Tl+ , or Ag+ , showing three clearly distinct coordination patterns depending on the cation used. The coordination to Cu+ leads to a complex in which the metalloligand is coordinated in a pincer form. The reaction with Tl+ affords a complex in which the ligand is acting as a Ï°2 -(trans)-chelate ligand. The reaction with Ag+ leads to a self-assembled structure, with two silver cations encased inside the cavity of a duplex structure formed by two self-assembled metallotweezers.

Chemically Tunable Formation of Different Discrete, Oligomeric, and Polymeric Self-Assembled Structures from Digold Metallotweezers.

Digold metallotweezers whose complex supramolecular landscape is controlled by adding a series of metal cations are described. The metallotweezers have a strong tendency to form interesting supramolecular structures on addition of Tl+ , Ag+ , and Cu+ . The choice of the cation can be used to direct the formation of a designated molecular architecture. The addition of thallium facilitates the formation of a self-aggregated duplex structure in which the cation occupies the cavity of the dimer. The same type of structure is formed when Cu+ is added, and the resulting duplex inclusion complex shows interesting vapochromic properties. This copper-encapsulating system evolves in solution to a 1D helical supramolecular polymer showing multiple aurophilic and Au⋅⋅⋅Cu interactions, in which the copper cation is bound to several alkynyl ligands of the tweezer. The addition of a small amount of silver cations to the digold tweezer yields a similar type of inclusion dimer complex, but adding an excess of the cation produces new discrete molecules presumably exhibiting multiple Au⋅⋅⋅Au, Au⋅⋅⋅Ag, and Ag⋅⋅⋅Ag metallophilic interactions. The differences in the supramolecular structures formed are ascribed to the different tendencies of the metal cations to exhibit interactions with the gold atoms and to coordinate to the alkynyl ligands of the tweezer.

Gold(I) Metallo-Tweezers for the Recognition of Functionalized Polycyclic Aromatic Hydrocarbons by Combined π-π Stacking and H-Bonding.

Two gold(I)-based metallo-tweezers with bis(Au-NHC) pincers and a carbazole connector have been obtained and used for the recognition of polycyclic aromatic hydrocarbons (PAHs). In the case of the tweezer with pyrene-NHC ligands, the presence of the pyrene fragment and the N-H bond in the carbazole linker enable the receptor to show significant enhanced binding abilities toward PAHs functionalized with H-bonding groups, through combined π-π stacking and H-bonding.

Cation-Driven Self-Assembly of a Gold(I)-Based Metallo-Tweezer.

A combination of self-complementary π-π-stacking interactions and metallophilic interactions triggered the self-assembly of a new digold(I) metallo-tweezer in the presence of several types of M+ ions. Titrations by fluorescence spectroscopy enabled the determination of the association constants of the resulting inclusion duplex complexes.

Polynuclear platinum phosphanido/phosphinito complexes: formation of P-O and P-O-P bonds through reductive coupling processes.

A mixture of the asymmetric complexes of formula [(RF)2Pt(µ-Ph2PO)(µ-PPh2)Pt(µ-PPh2)2Pt(solv)(solv')] [(1-(solv)(solv')] (solv, solv' = acetone, H2O, CH3CN) has been prepared by reaction of [(RF)2Pt(II)(µ-PPh2)2Pt(II)(µ-PPh2)2Pt(II)(NCCH3)2] with AgClO4 in CH3CN/acetone. The lability of the Pt-solvent bonds allows the displacement of the coordinated solvent molecules by dppm or Cl(-) and the isolation of the tri- or hexanuclear phosphanido/phosphinito Pt(ii) complexes [(C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(dppm)] (2) or [NBu4]2[(C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(µ-Cl)2Pt(µ-PPh2)2Pt(µ-PPh2)(µ-PPh2O)Pt(C6F5)2] (as a mixture of the two possible isomers 4a and 4b). Complex 2 reacts with AgClO4 to form the tetranuclear derivative [(C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(dppm)Ag(OClO3)] (3), which displays two Pt-Ag donor-acceptor bonds. The mixture of the hexanuclear isomers 4a-4b reacts with Tl(acac) producing the acetylacetonato complex [NBu4][(C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(acac)] (5) which, upon reaction with HCl, yields back the mixture of 4a-4b. The reaction of 4a-4b with PPh3 produces [NBu4][(C6F5)2Pt(µ-PPh2)(µ-PPh2O)Pt(µ-PPh2)2Pt(Cl)(PPh3)] (6) as a mixture of isomers with the chloro ligand located syn (6a) or anti (6b) to the PPh2O(-) group. Either the reaction of 6 with AgClO4 or the treatment of 5 with HPPh3ClO4 results in the formation of the species [(C6F5)2Pt(II)(µ-PPh2)2Pt(I)(µ-PPh2OPPh2)Pt(I)(PPh3)] (7) (44 VEC), which can be explained as the consequence of a PPh2O/PPh2 reductive coupling and a rearrangement of ligands in the molecule generating a Pt(ii),Pt(i),Pt(i) compound. All complexes were characterised in the solid state by XRD (only one of the isomers, in the cases of 4 and 6) and in solution by NMR spectroscopy.

Fluorescent Pyrene-Based Bis-azole Compounds: Synthesis and Photophysical Analysis.

A rational synthetic procedure for the preparation of a series of pyrene-based neutral and dicationic bis-azole compounds is reported. The method allows the tailored design of pyrene-based azoles with different substituents at the nitrogen atoms of the heterocycles, for which the relative conformation of the resulting bis-azoles can be easily controlled. The bis-azoliums were used for the preparation of the related diplatinum complexes by reaction with [{Pt(ppy)(µ-Cl)2 }2 ] (ppy=2-phenylpyridinate). The X-ray molecular structure of one of the resulting compounds, a diplatinum(II) bis(N-heterocyclic carbene) complex, is described. Studies on the photophysical properties of all new species are described. The emission of the bis-azole-based compounds seems to be independent of their substitution patterns, which basically indicates that physical properties such as solubility, melting point, and viscosity can be fine-tuned while maintaining the luminescence properties. Finally, the energies associated with the HOMO and LUMO levels suggest that this family provides versatility to match the energy levels of a wide range of host materials, which is important for the preparation of organic light-emitting devices.

An Extended Chain and Trinuclear Complexes Based on Pt(II)-M (M = Tl(I), Pb(II)) Bonds: Contrasting Photophysical Behavior.

The syntheses and structural characterizations of a Pt-Tl chain [{Pt(bzq)(C6F5)2}Tl(Me2CO)]n 1 and two trinuclear Pt2M clusters (NBu4)[{Pt(bzq)(C6F5)2}2Tl] 2 and [{Pt(bzq)(C6F5)2}2Pb] 3 (bzq = 7,8-benzoquinolinyl), stabilized by donor-acceptor Pt → M bonds, are reported. The one-dimensional heterometallic chain 1 is formed by alternate "Pt(bzq)(C6F5)2" and "Tl(Me2CO)" fragments, with Pt-Tl bond separations in the range of 2.961(1)-3.067(1) Å. The isoelectronic trinuclear complexes 2 (which crystallizes in three forms, namely, 2a, 2b, and 2c) and 3 present a sandwich structure in which the Tl(I) or Pb(II) is located between two "Pt(bzq)(C6F5)2" subunits. NMR studies suggest equilibria in solution implying cleavage and reformation of Pt-M bonds. The lowest-lying absorption band in the UV-vis spectra in CH2Cl2 and tetrahydrofuran (THF) of 1, associated with (1)MLCT/(1)L'LCT (1)[5dπ(Pt) → π*(bzq)]/(1)[(C6F5) → bzq], displays a blue shift in relation to the precursor, suggesting the cleavage of the chain maintaining bimetallic Pt-Tl fragments in solution, also supported by NMR spectroscopy. In 2 and 3, it shows a blue shift in THF and a red shift in CH2Cl2, supporting a more extensive cleavage of the Pt-M bonds in THF solutions than in CH2Cl2, where the trinuclear entities are predominant. The Pt-Tl chain 1 displays in solid state a bright orange-red emission ascribed to (3)MM'CT (M' = Tl). It exhibits remarkable and fast reversible vapochromic and vapoluminescent response to donor vapors (THF and Et2O), related to the coordination/decoordination of the guest molecule to the Tl(I) ion, and mechanochromic behavior, associated with the shortening of the intermetallic Pt-Tl separations in the chain induced by grinding. In frozen solutions (THF, acetone, and CH2Cl2) 1 shows interesting luminescence thermochromism with emissions strongly dependent on the solvent, concentration, and excitation wavelengths. The Pt2Tl complex 2 shows an emission close to 1, ascribed to charge transfer from the platinum fragment to the thallium [(3)(L+L')MM'CT]. 2 also shows vapoluminescent behavior in the presence of vapors of Me2CO, THF, and Et2O, although smaller and slower than those of 1. The trinuclear neutral complex Pt2Pb 3 displays a blue-shift emission band, tentatively assigned to admixture of (3)MM'CT (3)[Pt(d) → Pb(sp)] with some metal-mediated intraligand ((3)ππ/(3)ILCT) contribution. In contrast to 1 and 2, 3 does not show vapoluminescent behavior.

The challenge of deciphering linkage isomers in mixtures of oligomeric complexes derived from 9-methyladenine and trans-(NH3)2Pt(II) units.

Metal coordination to N9-substituted adenines, such as the model nucleobase 9-methyladenine (9MeA), under neutral or weakly acidic pH conditions in water preferably occurs at N1 and/or N7. This leads, not only to mononuclear linkage isomers with N1 or N7 binding, but also to species that involve both N1 and N7 metal binding in the form of dinuclear or oligomeric species. Application of a trans-(NH3)2Pt(II) unit and restriction of metal coordination to the N1 and N7 sites and the size of the oligomer to four metal entities generates over 50 possible isomers, which display different feasible connectivities. Slowly interconverting rotamers are not included in this number. Based on (1)H NMR spectroscopic analysis, a qualitative assessment of the spectroscopic features of N1,N7-bridged species was attempted. By studying the solution behavior of selected isolated and structurally characterized compounds, such as trans-[PtCl(9MeA-N7)(NH3)2]ClO4⋅2H2O or trans,trans-[{PtCl(NH3)2}2(9MeA-N1,N7)][ClO4]2⋅H2O, and also by application of a 9MeA complex with an (NH3)3Pt(II) entity at N7, [Pt(9MeA-N7)(NH3)3][NO3]2, which blocks further cross-link formation at the N7 site, basic NMR spectroscopic signatures of N1,N7-bridged Pt(II) complexes were identified. Among others, the trinuclear complex trans-[Pt(NH3)2{µ-(N1-9MeA-N7)Pt(NH3)3}2][ClO4]6⋅2H2O was crystallized and its rotational isomerism in aqueous solution was studied by NMR spectroscopy and DFT calculations. Interestingly, simultaneous Pt(II) coordination to N1 and N7 acidifies the exocyclic amino group of the two 9MeA ligands sufficiently to permit replacement of one proton each by a bridging heterometal ion, Hg(II) or Cu(II), under mild conditions in water.

Further orthometalated dinuclear palladium(III) compounds with bridging N,S-donor ligands.

New dinuclear palladium(III) compounds of general formula Pd2[(C6H4)PPh2]2[N-S]2Cl2, N-S being 2-mercaptopyridinate, 3a; 2-mercapto-6-methylpyridinate, 3b; 2-quinolinethiolate, 3c; 2-mercaptopyrimidinate, 3d; 1-methyl-1H-imidazole-2-thiolate, 3e; 1-methyl-1H-benzimidazole-2-thiolate, 3f; 2-mercaptobenzothiazolate, 3g and 5-mercapto-1-methyltetrazolate, 3h have been obtained by oxidation with PhICl2 of the corresponding palladium(II) counterparts. The stability of the new compounds has been studied by (31)P NMR spectroscopy from 200 to 298 K. Compounds 3f-h were relatively stable until room temperature and they have been synthesized and characterized by (31)P, (1)H and (13)C NMR spectroscopy at 223 K. Compound 3h was also structurally characterized by single X-ray diffraction methods at 150 K showing a Pd-Pd distance of 2.6334(6) Å. A topological charge density analysis has also been performed in order to obtain information on the nature of the bonding in these new palladium(II) and (III) compounds. The contribution of the sulphur p orbitals to the HOMO orbitals in the oxidized compounds allows greater stabilization.