Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments.

The "precursor approach" has proved particularly valuable for the preparation of insoluble and unstable π-conjugated polycyclic compounds (π-CPCs), which cannot be synthesized via in-solution organic chemistry, for their improved processing, as well as for their electronic investigation both at the material and single-molecule scales. This method relies on the synthesis and processing of soluble and stable direct precursors of the target π-CPCs, followed by their final conversion in situ, triggered by thermal activation, photoirradiation or redox control. Beside well-established reactions involving the elimination of carbon-based small molecules, i.e., retro-Diels-Alder and decarbonylation processes, the late-stage extrusion of chalcogen fragments has emerged as a highly promising synthetic tool to access a wider variety of π-conjugated polycyclic structures and thus to expand the potentialities of the "precursor approach" for further improvements of molecular materials' performances. This review gives an overview of synthetic strategies towards π-CPCs involving the ultimate elimination of chalcogen fragments upon thermal activation, photoirradiation and electron exchange.

Extended Tripodal Hydrotris(indazol-1-yl)borate Ligands as Ruthenium-Supported Cogwheels for On-Surface Gearing Motions.

This paper reports the synthesis of ruthenium-based molecular gear prototypes composed of a brominated or non-brominated pentaphenylcyclopentadienyl ligand as an anchoring unit and a tripodal ligand with aryl-functionalized indazoles as a rotating cogwheel. Single crystal structures of the ruthenium complexes revealed that the appended aryl groups increase the apparent diameter of the cogwheel rendering them larger than the diameter of the anchoring units and consequently making them suitable for intermolecular gearing motions once the complexes will be adsorbed on a surface.

Divergent Synthesis of Molecular Winch Prototypes.

We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties.

Molecular Gears: From Solution to Surfaces.

This review highlights the major efforts devoted to the development of molecular gears over the past 40 years, from pioneering covalent bis-triptycyl systems undergoing intramolecular correlated rotation in solution, to the most recent examples of gearing systems anchored on a surface, which allow intermolecular transmission of mechanical power. Emphasis is laid on the different strategies devised progressively to control the architectures of molecular bevel and spur gears, as intramolecular systems in solution or intermolecular systems on surfaces, while aiming at increased efficiency, complexity and functionality.

Molecular Rotor Functionalized with a Photoresponsive Brake.

A molecular motor that has been previously shown to rotate when fueled by electrons through a scanning tunneling microscope tip has been functionalized with a terarylene photochrome fragment on its rotating subunit. Photoisomerization has been performed under UV irradiation. Variable-temperature 1H NMR and UV-vis studies demonstrate the rotational motion and its braking action after photoisomerization. The braking action can be reversed by thermal heating. Once the rigid and planar closed form is obtained, the rotation is effectively slowed at lower temperature, making this new rotor a potential motor with an independent response to electrons and light.

Photophysical properties of 1,2,3,4,5-pentaarylcyclopentadienyl-hydrotris(indazolyl)borate ruthenium(II) complexes.

The photophysical properties of heteroleptic rotor-like Ru(ii) complexes containing both a cyclopentadienyl-type ligand and a hydrotris(indazolyl)borate chelating unit with a piano stool structure (Ar5L1-Ru-S1 and L3-Ru-S1) and their corresponding subunits have been investigated. The complexes show peculiar absorption features when compared with their related ligands or fragments. L3-Ru-S1 was found to be non-emissive, while Ar5L1-Ru-S1 showed a weak emission with a quantum yield of 0.27%. With the help of DFT calculations, we demonstrate that the new absorption features can be attributed to ruthenium-based charge transfer transitions which involve the π* orbitals of the phenyl substituents of the cyclopentadienyl ligand.

Dipolar Nanocars Based on a Porphyrin Backbone.

Invited for the cover of this issue is Gwénaël Rapenne and co-workers from CEMES-CNRS at University Paul Sabatier, Toulouse, France and from NAIST, Nara, Japan. The image depicts an artistic representation of a nanocar race. Read the full text of the article at 10.1002/chem.202001999.

Dipolar Nanocars Based on a Porphyrin Backbone.

The design and synthesis of a new family of nanocars is reported. To control their motion, we integrated a dipole which can be tuned thanks to strategic donor and acceptor substituents at the 5- and 15-positions of the porphyrin backbone. The two other meso positions are substituted with ethynyltriptycene moieties which are known to act as wheels. Full characterization of nine nanocars is presented as well as the electrochemistry of these push-pull molecules. DFT calculations allowed us to evaluate the magnitude of the dipoles and to understand the electrochemical behavior and how it is affected by the electron donating and accepting groups present. An X-ray crystal structure of one nanocar has also been obtained.

Star-Shaped Ruthenium Complexes as Prototypes of Molecular Gears.

The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length.

From the Synthesis of Nanovehicles to Participation in the First Nanocar Race-View from the French Team.

This review article presents our accomplished work on the synthesis of molecular triptycene wheels and their introduction into nanovehicles such as wheelbarrows and nanocars, equipped with two and four wheels, respectively. The architecture of nanovehicles is based on polycyclic aromatic hydrocarbons, which provide a potential cargo zone. Our strategy allowed us to obtain planar or curved nanocars, exhibiting different mobilities on metallic surfaces. Our curved nanocar participated in the first nanocar race organized in Toulouse (France) on 28 and 29 April 2017.

Synthesis of γ-lactams and γ-lactones via intramolecular Pd-catalyzed allylic alkylations.

CONSPECTUS: Lactones and lactams are a well-known class of natural products and can be used as building blocks in organic synthesis. In addition, they can be found in many natural sources and synthetic drugs and have a broad range of biological or odorant properties. Chemists can create these useful compounds through palladium catalysis, which is a highly efficient tool for organic synthesis and is conveniently functional group tolerant. In this Account, we describe our work over the past 15 years in intramolecular Pd-catalyzed allylations where we have tethered the nucleophile and the electrophile by either an amide or an ester moiety, to produce γ-lactams and γ-lactones. We discuss in detail how the nature of the heteroatom tether influences the regioselectivity of the reaction. For example, a ketone [-C(O)CH2-] tether leads to mixtures of 5-exo and 7-endo cyclization products, while ester or amide [-C(O)X-] tethers afford sole 5-exo products. However, in the case of X = O, we were required to overcome two issues in the synthesis of γ-lactones. First of all, the tethering ester function can compete with the allylic leaving group in the oxidative addition to the Pd(0) center. Second, in this case, the proportion of the conformers that have a suitable geometry for cyclization is very low. When we insert a juxtaposed silyl group on the allyl fragment, the molecule can undergo oxidative addition and functionalization of the lactone via Hiyama cross-coupling. We also performed DFT calculations on these systems, which allowed us to better understand the behavior of [-C(O)X-] and [-C(O)CH2-] tethers. Computations also let us rationalize the different reactivities that we observed as a function of the geometry (Z or E) of the starting substrates. In addition, we were able to synthesize natural products or analogs (α-kainic acid, isoretronecanol, and picropodophyllin). We could turn these allylation reactions into asymmetric transformations and incorporate them into domino sequences. Thus, an allylation/Mizoroki-Heck sequence allowed us to straightforwardly access an aza-analog of picropodophyllin, as well as reach the lysergic acid backbone. Finally, we found that through carbopalladation of allenes, we could efficiently synthesize the key η(3)-allylpalladium intermediates that were then ready for allylation reactions.

Synthesis of Functionalized Mono-, Bis-, and Trisethynyltriptycenes for One-Dimensional Self-Assembly on Surfaces.

This paper describes the synthesis of triptycene-based building blocks that are able to interact through hydrogen bonds to form one-dimensional self-assembled motifs on surfaces. We designed 9,10-diethynyltriptycene derivatives functionalized at the ethynyl end groups by a variety of hydrogen-bonding groups for homomolecular recognition and complementary building blocks for heteromolecular recognition. We also present the synthesis of bis- and trisethynyltriptycenes with terminal alkyne functional groups available for on-surface azide-alkyne cycloaddition reaction to expand the potential of the triptycene building block.

Aryl Sulfoxides: A Traceless Directing Group for Catalytic C-H Activation of Arenes.

The transition metal-catalyzed C-H activation of arenes directed by sulfoxides represents a compelling strategy in organic synthesis, owing to its exceptional regioselectivity and high efficiency. This innovative approach stands out for its traceless character, enabling the direct functionalization of arenes, before the easy removal or conversion of the key sulfinyl moiety. Beyond their utility as a directing group, sulfoxides have proved particularly valuable to mediate as chiral auxiliaries, presenting exciting prospects for the synthesis of stereo-enriched compounds upon C-H functionalization. The versatility demonstrated by the method paves the way to different structures with potential applications ranging from medicinal chemistry to organic electronics.

Copper-catalysed perarylation of cyclopentadiene: synthesis of hexaarylcyclopentadienes.

While hexaphenylsilacyclopentadiene (hexaphenylsilole) is viewed as an archetypal Aggregation-Induced Emission (AIE) luminogen, its isostructural hydrocarbon surrogate hexaphenylcyclopentadiene has strikingly never been investigated in this context, most probably due to a lack of synthetic availability. Herein, we report a straightforward synthesis of hexaphenylcyclopentadiene, via the direct perarylation of cyclopentadiene upon copper(i) catalysis under microwave activation, with the formation of six new C-C bonds in a single synthetic operation. Using zirconocene dichloride as a convenient source of cyclopentadiene and a variety of aryl iodides as coupling partners, this copper-catalysed cross-coupling reaction gave rise to a series of unprecedented hexaarylcyclopentadienes. The latter are direct precursors of extended π-conjugated polycyclic compounds, and their cyclodehydrogenation under Scholl reaction conditions yielded helicenic 17,17-diarylcyclopenta[l,l']diphenanthrenes. These structurally complex polyannelated fluorene derivatives can now be prepared in only two synthetic steps from cyclopentadiene.

Desymmetrised pentaporphyrinic gears mounted on metallo-organic anchors.

Mastering intermolecular gearing is crucial for the emergence of complex functional nanoscale machineries. However, achieving correlated motion within trains of molecular gears remains highly challenging, due to the multiple degrees of freedom of each cogwheel. In this context, we designed and synthesised a series of star-shaped organometallic molecular gears incorporating a hydrotris(indazolyl)borate anchor to prevent diffusion on the surface, a central ruthenium atom as a fixed rotation axis, and an azimuthal pentaporphyrinic cyclopentadienyl cogwheel specifically labelled to monitor its motion by non-time-resolved Scanning Tunneling Microscopy (STM). Desymmetrisation of the cogwheels was first achieved sterically, i.e. by introducing one tooth longer than the other four. For optimal mechanical interactions, chemical labelling was also investigated as a preferential way to induce local contrast in STM images, and the electronic properties of one single paddle were modulated by varying the porphyrinic scaffold or the nature of the central metal. To reach such a structural diversity, our modular synthetic approach relied on sequential cross-coupling reactions on a penta(p-halogenophenyl)cyclopentadienyl ruthenium(ii) key building block, bearing a single pre-activated p-iodophenyl group. Chemoselective Sonogashira or more challenging Suzuki-Miyaura reactions allowed the controlled introduction of the tagged porphyrinic tooth, and the subsequent four-fold cross-couplings yielded the prototypes of pentaporphyrinic molecular gears for on-surface studies, incorporating desymmetrised cogwheels over 5 nm in diameter.

Ruthenium complexes of sterically-hindered pentaarylcyclopentadienyl ligands.

The synthesis of ruthenium complexes incorporating an overcrowded pentaarylcyclopentadienyl ligand has been investigated, and higher efficiency has been reached using chlorine-functionalised precursors when compared with their brominated counterparts. A new methodology for the preparation of chlorocyclopentadienes has been developed which is well adapted for highly sterically hindered compounds and works with either electron rich or poor systems.

Transmitting Stepwise Rotation among Three Molecule-Gear on the Au(111) Surface.

The realization of a train of molecule-gears working under the tip of a scanning tunneling microscope (STM) requires a stable anchor of each molecule to the metal surface. Such an anchor can be promoted by a radical state of the molecule induced by a dissociation reaction. Our results, rationalized by density functional theory calculations, reveal that such an open radical state at the core of star-shaped pentaphenylcyclopentadiene (PPCP) favors anchoring. Furthermore, to allow the transmission of motion by STM manipulation, the molecule-gears should be equipped with specific groups facilitating the tip-molecule interactions. In our case, a tert-butyl group positioned at one tooth end of the gear benefits both the tip-induced manipulation and the monitoring of rotation. With this optimized molecule, we achieve reproducible and stepwise rotations of the single gears and transmit rotations for up to three interlocked units.

Phosphine-free palladium-catalyzed allene carbopalladation/allylic alkylation domino sequence: a new route to 4-(alpha-styryl) gamma-lactams.

Free to decide: Various 4-(alpha-styryl) gamma-lactams are synthesized in 61-88% yield by a phosphine-free palladium-catalyzed carbopalladation/allylic alkylation domino sequence (see scheme). The cyclization is totally regio- and diastereoselective in favor of the 3,4-trans-disubstituted gamma-lactam. The process is successfully applied to the synthesis of a new aza analogue of the naturally occurring lignan (+)-oxo-parabenzlactone.

Modular synthesis of pentaarylcyclopentadienyl Ru-based molecular machines via sequential Pd-catalysed cross couplings.

A dissymmetric piano-stool ruthenium(ii) complex bearing different halogens on the rotor part was efficiently prepared and subsequently used as a key building block in the modular synthesis of potential rotative molecular machines via palladium-catalysed "Sonogashira/Suzuki-Miyaura" sequences. Applying this novel synthetic route to various cross-coupling partners, prototypes of molecular winches and cogwheels for gear applications, specifically designed for studies at the single-molecule scale, were efficiently obtained.

A chiral molecular propeller designed for unidirectional rotations on a surface.

Synthetic molecular machines designed to operate on materials surfaces can convert energy into motion and they may be useful to incorporate into solid state devices. Here, we develop and characterize a multi-component molecular propeller that enables unidirectional rotations on a material surface when energized. Our propeller is composed of a rotator with three molecular blades linked via a ruthenium atom to a ratchet-shaped molecular gear. Upon adsorption on a gold crystal surface, the two dimensional nature of the surface breaks the symmetry and left or right tilting of the molecular gear-teeth induces chirality. The molecular gear dictates the rotational direction of the propellers and step-wise rotations can be induced by applying an electric field or using inelastic tunneling electrons from a scanning tunneling microscope tip. By means of scanning tunneling microscope manipulation and imaging, the rotation steps of individual molecular propellers are directly visualized, which confirms the unidirectional rotations of both left and right handed molecular propellers into clockwise and anticlockwise directions respectively.