Cyclometalated luminescent platinum(II) complexes of dissymmetrical 2,2':4',2''-terpyridine and its self-assembled dimer presenting Pt-Ag dative bonds.

A series of cyclometalated (N^C^N) Pt(II)-platinum complexes featuring a terpyridine ligand with a non-coordinating nitrogen atom and a Pt-C bond was synthesized. In the presence of Ag+, the bis(isonitrile)Pt(II) complex formed a remarkable self-assembled helicoidal dimer stabilized by coordination of Ag(I) and metallophilic Pt-Ag interactions. Its assembly was observed in the solid state and maintained in solution. All complexes show strong luminescence and multiple emitting states, which could be rationalized based on solid state X-ray structures and coordinating environment.

Switchable molecular tweezers: design and applications.

Switchable molecular tweezers are a unique class of molecular switches that, like their macroscopic analogs, exhibit mechanical motion between an open and closed conformation in response to stimuli. Such systems constitute an essential component of artificial molecular machines. This review will present selected examples of switchable molecular tweezers and their potential applications. The first part will be devoted to chemically responsive tweezers, including stimuli such as pH, metal coordination, and anion binding. Then, redox-active and photochemical tweezers will be presented.

Size-dependent compression of threaded alkyldiphosphate in head to head cyclodextrin [3]pseudorotaxanes.

The encapsulation of guests in a confined space enables unusual conformations and reactivities. In particular, the compression of akyl chains has been obtained by self-assembled molecular capsules but such an effect has not been reported in solution for pseudorotaxane architectures. By exploiting the tendency of cyclodextrin (CD) to form head to head [3]pseudorotaxanes and the hydrogen bonding abilities of phosphate groups, we have studied the effect of the CD dimer cavity on the conformation of threaded α,ω-alkyl-diphosphate axles. The formation of [2]pseudorotaxanes and [3]pseudorotaxanes was investigated by a combination of NMR, ITC and X-ray diffraction techniques. In the solid state, the [3]pseudorotaxane with a C8 axle presents a fully extended conformation with both terminal phosphate groups interacting with hydroxyl groups of the primary rim of CDs. Such hydrogen bonding interactions are also present with the C9 and C10 axles resulting in a compression of the alkyl chain with gauche conformations in the solid state. NMR studies have shown that this effect is maintained in solution resulting in a size-dependent progressive compression of the alkyl chain by the CD [3]pseudorotaxane architecture for C9, C10 and C11 axles.

Precise Rate Control of Pseudorotaxane Dethreading by pH-Responsive Selectively Functionalized Cyclodextrins.

A family of cyclodextrins functionalized with zero, one, two, or six amines was shown to control the rate of their threading and dethreading on a molecular axle depending on the pH and their substitution pattern. The originality of this system lies in the rate control of the switch by operating the stimulus directly on the macrocycle.

Dual switchable molecular tweezers incorporating anisotropic MnIII-salphen complexes.

An alternative strategy for the synthesis of terpyridine based switchable molecular tweezers has been developed to incorporate anisotropic Mn(iii)-salphen complexes. The free ligand was synthesized using a building block strategy based on Sonogashira coupling reactions and was then selectively metalated with manganese in a last step. The conformation of the tweezers was switched from an open 'W' shaped form to a closed 'U' form by Zn(ii) coordination to the terpyridine unit bringing the two Mn-salphen moieties in close spatial proximity as confirmed by X-ray crystallography. An alternate switching mechanism was observed by the intercalation of a bridging cyanide ligand between the two Mn-salphen moieties that resulted in the closing of the tweezers. These dual stimuli are attractive for achieving multiple controls of the mechanical motion of the tweezers. A crystallographic structure of unexpected partially oxidized closed tweezers was also obtained. One of the two Mn-salphen moieties underwent a ligand-centered oxidation of an imino to an amido group allowing an intramolecular Mn-Oamide-Mn linkage. The magnetic properties of the manganese(iii) dimers were investigated to evaluate the magnetic exchange interaction and analyze the single molecule magnet behavior.

Synthesis and Guest Recognition of Switchable Pt-Salphen Based Molecular Tweezers.

Molecular tweezers are artificial receptors that have an open cavity generated by two recognition units pre-organized by a spacer. Switchable molecular tweezers, using a stimuli-responsive spacer, are particularly appealing as prototypes of the molecular machines that combine mechanical motion and allosteric recognition properties. In this present study, the synthesis of switchable molecular tweezers composed of a central terpyridine unit substituted in 4,4″ positions by two Pt(II)-salphen complexes is reported. The terpyridine ligand can be reversibly converted upon Zn(II) coordination from a free 'U'-shaped closed form to a coordinated 'W' open form. This new substitution pattern enables a reverse control of the mechanical motion compared to the previously reported 6,6″ substituted terpyridine-based tweezers. Guest binding studies with aromatic guests showed an intercalation of coronene in the cavity created by the Pt-salphen moieties in the closed conformation. The formation of 1:1 host-guest complex was investigated by a combination of NMR studies and DFT calculations.

Six States Switching of Redox-Active Molecular Tweezers by Three Orthogonal Stimuli.

A six level molecular switch based on terpyridine(Ni-salphen)2 tweezers and addressable by three orthogonal stimuli (metal coordination, redox reaction, and guest binding) is reported. By a metal coordination stimulus, the tweezers can be mechanically switched from an open "W"-shaped conformation to a closed "U"-shaped form. Theses two states can each be reversibly oxidized by the redox stimulus and bind to a pyrazine guest resulting in four additional states. All six states are stable and accessible by the right combination of stimuli and were studied by NMR, XRD, EPR spectroscopy, and DFT calculations. The combination of the supramolecular concepts of mechanical motion and guest binding with the redox noninnocent and valence tautomerism properties of Ni-salphen complexes added two new dimensions to a mechanical switch.

Mechanostereoselective One-Pot Synthesis of Functionalized Head-to-Head Cyclodextrin [3]Rotaxanes and Their Application as Magnetic Resonance Imaging Contrast Agents.

A versatile, five-component, one-pot synthesis of cyclodextrin (CD) [3]rotaxanes using copper-catalyzed azide-alkyne cycloaddition has been developed. Head-to-head [3]rotaxanes of α-CD selectively functionalized by one or two gadolinium 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid monoamide complexes were obtained mechanostereoselectively. The magnetic resonance imaging efficiency, expressed by the longitudinal proton relaxivity of the rotaxanes, was significantly improved as compared to the functionalized CD. In vitro and in vivo preclinical studies showed a higher contrast and retention in the kidney than gadolinium 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid complex, demonstrating the potential of these rotaxanes as MRI contrast agent.

Mechanical switching of magnetic interaction by tweezers-type complex.

A control of the interaction between two spin centers was achieved by using a mechanical motion in a terpy(Cu-salphen)2 complex. Upon coordination a conformation change and switching from a paramagnetic to an antiferromagnetically coupled system was observed by EPR and SQUID measurements.

Switchable platinum-based tweezers with Pt-Pt bonding and selective luminescence quenching.

Molecular tweezers incorporating peripheral platinum salphen complexes and a central chelating terpyridine group have been synthesized. The terpyridine can be switched upon metal binding between a free 'W' shaped form and a coordinated 'U' form. The crystallographic structure of the zinc-closed molecular tweezers was obtained and presented a strong π-stacking between the Pt-salphen units associated with a Pt-Pt bond. The luminescence properties, notably in response to selected guest ions (Zn(2+), Pb(2+), Hg(2+)) and the resulting mechanical motion, have been investigated by UV-Vis and emission spectroscopy. While ion coordination to the terpy resulted in no significant changes in the luminescence, a selective intercalation of a second Hg(2+) associated with a large differential quenching was observed.

Terpy(Pt-salphen)2 switchable luminescent molecular tweezers.

The design and synthesis of switchable molecular tweezers based on a luminescent terpy(Pt-salphen)2 (1; terpy=terpyridine) complex is reported. Upon metal coordination, the tweezers can switch from an open "W"-shaped conformation to a closed "U"-shaped form that is adapted for selective recognition of cations. Closing of the tweezers by metal coordination (M=Zn(2+), Cu(2+), Pb(2+), Fe(2+), Hg(2+)) was monitored by (1)H NMR and/or UV/Vis titrations. During the titration, exclusive formation of the 1:1 complex [M(1)] was observed, without appearance of an intermediate 1:2 complex [M(1)2]. The crystallographic structure of the 1:1 complex was obtained with Pb(2+) and showed a distorted helical structure. Selective intercalation of Hg(2+) cations by the closed "U" form was observed. The tweezers were reopened by selective metal decoordination of the terpyridine ligand by using tris(2-aminoethyl)amine (tren) as a competitive ligand without modification of the Pt-salphen complex. Detailed photophysical studies were performed on the open and closed tweezers. Structured emission was observed in the open form from the Pt-salphen moieties, with a high quantum yield and a long lifetime. The emission is slightly modified upon closing with 1 equivalent of Zn(2+) or Hg(2+), whereas a dramatic quenching was obtained upon intercalation of additional Hg(2+).

Cyclodextrin polyrotaxanes as a highly modular platform for the development of imaging agents.

Selectively functionalized cyclodextrins with a bodipy fluorescent tag or Gd(3+) complex were synthetized and threaded onto a polyammonium chain to form polyrotaxanes. This modular supramolecular assembly makes an ideal platform for bimodal (fluorescent and MRI) imaging applications.

Dynamics of ion-regulated photoinduced electron transfer in BODIPY-BAPTA conjugates.

Efficient Ca(2+)-switched fluorescent sensors, where fluorescence output is governed by a light-activated ion-gated electron transfer pathway, can be obtained on combining BODIPY chromophores with a readily oxidized biocompatible and selective BAPTA receptor. Herein we report the synthesis and studies of two such conjugates, which vary in the nature of the spacer separating the two electroactive components, namely none (1) or phenyl (2). Single crystal X-ray crystallography and molecular modelling structures and calculations give information on molecular and electronic structure, while steady-state fluorescence experiments show high Ca(2+)-induced fluorescence enhancement factors of 122 and 23 and K(d) values of 0.50 µM and 0.13 µM for 1 and 2, respectively. Notably, studies of the ultrafast photoinduced processes (through transient absorption spectroscopy) give access to electron transfer dynamics in pseudo-physiological media as well as in a polar non-protic solvent and information about the fate of the excited molecules in the presence and absence of calcium. In water, electron transfer rates as high as 3.3 × 10(12) s(−1) and 8.3 × 10(11) s(−1) are measured for the ion-free, directly connected conjugate and the variant incorporating a phenyl spacer, respectively. This electron transfer pathway is efficiently blocked by the presence of an ion, restoring fluorescence.

Facile functionalization of a fully fluorescent perfluorophenyl BODIPY: photostable thiol and amine conjugates.

Selective nucleophilic substitution on a perfluorophenyl unit comprising a BODIPY fluorophore using an alkanethiol or a primary amine offers a quantitative fluorophore labelling strategy, while retaining high photostability and emission quantum yields approaching unity.

Toward chemical propulsion: synthesis of ROMP-propelled nanocars.

The synthesis and ring-opening metathesis polymerization (ROMP) activity of two nanocars functionalized with an olefin metathesis catalyst is reported. The nanocars were attached to a Hoveyda-Grubbs first- or second-generation metathesis catalyst via a benzylidene moiety. The catalytic activity of these nanocars toward ROMP of 1,5-cyclooctadiene was similar to that of their parent catalysts. The activity of the Hoveyda-Grubbs first-generation catalyst-functionalized nanocar was further tested with polymerization of norbornene. Hence, the prospect is heightened for a ROMP process to propel nanocars across a surface by providing the translational force.

Synthesis of fluorescent dye-tagged nanomachines for single-molecule fluorescence spectroscopy.

In an effort to elucidate the mechanism of movement of nanovehicles on nonconducting surfaces, the synthesis and optical properties of five fluorescently tagged nanocars are reported. The nanocars were specifically designed for studies by single-molecule fluorescence spectroscopy and bear a tetramethylrhodamine isothiocyanate fluorescent tag for excitation at 532 nm. The molecules were designed such that the arrangement of their molecular axles and p-carborane wheels relative to the chassis would be conducive to the control of directionality in the motion of these nanovehicles.

Synthesis of highly fluorescent BODIPY-based nanocars.

The convergent synthesis of inherently highly fluorescent nanocars incorporating 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-containing axles and p-carborane wheels is reported. These nanocars are expected to exhibit rolling motion with predetermined patterns over smooth surfaces, depending on their chassis. Their quantum yields of fluorescence (Phi(F) > 0.7) make them excellent candidates for imaging and tracking by single-molecule fluorescence microscopy. An analogue as a stationary control with tert-butyl groups instead of p-carborane wheels was also synthesized.

Molecular machinery: synthesis of a "nanodragster".

The synthesis and imaging by scanning tunneling microscopy of a mixed wheeled nanovehicle composed of a p-carborane small-wheeled short front axle and a C(60) large-wheeled long rear axle that has been termed a nanodragster due to the structural relation to a dragster are reported. This nanodragster is expected to exhibit motion at a lower temperature than pure C(60)-wheeled nanocars and should allow the investigation of the role played by p-carborane wheels in directional motion.

Fullerene/thiol-terminated molecules.

A series of fullerene-terminated oligo(phenylene ethynylene) (OPEs) have been synthesized for potential use in electronic or optoelectronic device monolayers. Electronic properties such as the energy levels and the distribution of HOMOs and LUMOs of fullerene-terminated OPEs have been calculated using the ab initio method at the B3LYP/6-31G(d) level. The calculations have revealed the concentration of frontier orbitals on the fullerene cage and a narrow distribution of HOMO-LUMO energy gaps. Ultraviolet photoelectron spectroscopy and inverse photoemission spectroscopy studies have been performed to further examine the electronic properties of the fullerene-terminated OPEs on gold surfaces. The obtained broad photoelectron spectra suggest that there are strong intermolecular interactions in the fullerene self-assembled monolayers, and the small bandgap (approximately 1.5 eV), determined by the photoelectron spectroscopy, indicates the unique nature of the fullerene-terminated OPEs in which the C(60) moiety can be connected to the Au surface through the conjugated OPE backbone.

Prototypes of molecular motors based on star-shaped organometallic ruthenium complexes.

This tutorial review presents our strategy to control the rotation in a molecular rotary motor, and the family of star-shaped ruthenium complexes designed to perform such a task. The molecules have a piano-stool structure with a "stator" meant to be grafted on a surface, and a "rotor" bearing redox-active groups, so that addressing the molecule with nano-electrodes would trigger rotation.