Ytterbium(III) Complex with Photochromic Ruthenium(II) Acetylide Ligand: All Visible Light Photoswitching of NIR Luminescence.

We report a ruthenium(II) bisacetylide complex bearing a photochromic dithienylethene (DTE) acetylide arm and a coordinating bipyridyl on the trans acetylide unit. Its coordination with Yb(TTA)3 centers (TTA = 2-thenoyltrifluoroacetonate) produces a bimetallic complex in which the dithienylethene isomerization is triggered by both ultraviolet (UV) light absorbed by the DTE unit and 450 nm excitation in a transition of the organometallic moiety. The redox behavior arising from the ruthenium(II) bisacetylide system is fully investigated by cyclic voltammetry and spectroelectrochemistry, revealing a lack of stability of the DTE-closed oxidized state preventing effective redox luminescence switching. On the other hand, the photoswitching of ytterbium(III) near-infrared (NIR) emission triggered by the photochromic reaction is fully operational. The electronic structure of this complex in its different states characterized by strong electronic coupling between the DTE and the ruthenium(II)-based moieties leading to metal-assisted photochromic behavior were rationalized with the help of time-dependent density functional theory (TD-DFT) calculations.

Tunable Symmetry-Breaking-Induced Dual Functions in Stable and Photoswitched Single-Molecule Junctions.

The aim of molecular electronics is to miniaturize active electronic devices and ultimately construct single-molecule nanocircuits using molecules with diverse structures featuring various functions, which is extremely challenging. Here, we realize a gate-controlled rectifying function (the on/off ratio reaches ∼60) and a high-performance field effect (maximum on/off ratio >100) simultaneously in an initially symmetric single-molecule photoswitch comprising a dinuclear ruthenium-diarylethene (Ru-DAE) complex sandwiched covalently between graphene electrodes. Both experimental and theoretical results consistently demonstrate that the initially degenerated frontier molecular orbitals localized at each Ru fragment in the open-ring Ru-DAE molecule can be tuned separately and shift asymmetrically under gate electric fields. This symmetric orbital shifting (AOS) lifts the degeneracy and breaks the molecular symmetry, which is not only essential to achieve a diode-like behavior with tunable rectification ratio and controlled polarity, but also enhances the field-effect on/off ratio at the rectification direction. In addition, this gate-controlled symmetry-breaking effect can be switched on/off by isomerizing the DAE unit between its open-ring and closed-ring forms with light stimulus. This new scheme offers a general and efficient strategy to build high-performance multifunctional molecular nanocircuits.

Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets.

A one-dimensional coordination solid 1c is synthesized by reaction of a bispyridyl dithienylethene (DTE) photochromic unit with the highly anisotropic dysprosium-based single-molecule magnet [Dy(Tppy)F(pyridine)2]PF6. Slow magnetic relaxation characteristics are retained in the chain compound 1c, and photoisomerization of the bridging DTE ligand induces a single-crystal-to-single-crystal transformation that can be monitored using photocrystallography. Notably, the resulting chain compound 1o exhibits faster low-temperature relaxation than that of 1c, which is apparent in magnetic hysteresis data collected for both compounds as high as 4 K. Ab initio calculations suggest that this photomodulation of the magnetic relaxation behavior is due to crystal packing changes rather than changes to the crystal field splitting upon ligand isomerization.

Dual Light and Redox Control of NIR Luminescence with Complementary Photochromic and Organometallic Antennae.

With the help of a judicious association between dithienylethene (DTE) units, an ytterbium ion, and a ruthenium carbon-rich complex, we describe (i) the efficient (on/off) switching of pure NIR luminescence with a photochromic unit absorbing in the UV range and (ii) the association of electrochemical and photochemical control of this NIR emission in a single system with nondestructive readout.

Self-Assembled Monolayers of Redox-Active 4d-4f Heterobimetallic Complexes.

In this work, we report the preparation of functional interfaces incorporating heterobimetallic systems consisting in the association of an electroactive carbon-rich ruthenium organometallic unit and a luminescent lanthanide ion (Ln = Eu3+ and Yb3+). The organometallic systems are functionalized with a terminal hexylthiol group for subsequent gold surface modification. The formation of self-assembled monolayers (SAMs) with these complex molecular architectures are thoroughly demonstrated by employing a combination of different techniques, including infrared reflection absorption spectroscopy, ellipsometry, contact angle, and cyclic voltammetry measurements. The immobilized heterobimetallic systems show fast electron-transfer kinetics and, hence, are capable of fast electrochemical response. In addition, the characteristic electrochemical signals of the SAMs were found to be sensitive to the presence of lanthanide centers at the bipyridyl terminal units. A positive shift of the potential of the redox signal is readily observed for lanthanide complexes compared to the bare organometallic ligand. This effect is equally observed for preformed complexes and on-surface complexation. Thus, an efficient ligating recruitment of europium and ytterbium cations at gold-modified electrodes is demonstrated, allowing for an easy electrochemical detection of the lanthanide ions along with an alternative preparative method of SAMs incorporating lanthanide cations compared to the immobilization of the preformed complex.

A Terminal Fluoride Ligand Generates Axial Magnetic Anisotropy in Dysprosium Complexes.

The first dysprosium complexes with a terminal fluoride ligand are obtained as air-stable compounds. The strong, highly electrostatic dysprosium-fluoride bond generates a large axial crystal-field splitting of the J=15/2 ground state, as evidenced by high-resolution luminescence spectroscopy and correlated with the single-molecule magnet behavior through experimental magnetic susceptibility data and ab initio calculations.

Dual-Responsive Molecular Switches Based on Dithienylethene-RuII Organometallics in Self-Assembled Monolayers Operating at Low Voltage.

Two carbon-rich ruthenium complexes bearing a dithienylethene (DTE) unit and a hexylthiol spacer were designed to be attached on gold surfaces. Both compounds display photochemically driven switching properties, allowing reversible conversion from open to closed forms of the DTE units upon irradiation in solution. In contrast, only the bimetallic complex undergoes an efficient electrochemical ring closure at low potential, (0.5 V vs. SCE), whereas the monometallic complex shows a simple one-electron reversible redox event. These appealing switching properties could be successfully transferred within diluted self-assembled monolayers (SAMs). Furthermore, the two immobilized organometallics exhibit fast electron-transfer kinetics. Therefore, this organometallic strategy allows us to obtain multifunctional surfaces with the possibility of combining switching events triggered by an electrochemical oxidation at low potential and by light at distinct wavelengths for a write-and-erase function, along with an access to different oxidation states. Importantly, a non-destructive electrochemical read-out is achieved at a sufficiently high scan rate that prevents any electrochemical closing. On the whole, the two surface-confined organometallic compounds exhibit appealing properties for application in molecular electronics.

Ruthenium Carbon-Rich Group as a Redox-Switchable Metal Coupling Unit in Linear Trinuclear Complexes.

The preparation and properties of novel ruthenium carbon-rich complexes [(Ph-C≡C-)2-nRu(dppe)2(-C≡C-bipyM(hfac)2)n] (n = 1, 2; M = CuII, MnII; bipy = 2,2'-bipyridin-5-yl) characterized by single-crystal X-ray diffraction and designed for molecular magnetism are reported. With the help of EPR spectroscopy, we show that the neutral ruthenium system sets up a magnetic coupling between two remote paramagnetic CuII units. More specifically, these copper compounds are unique examples of bimetallic and linear heterotrimetallic compounds for which a complete rationalization of the magnetic interactions could be made for exceptionally long distances between the spin carriers (8.3 Å between adjacent Cu and Ru centers, 16.6 Å between external Cu centers) and compared at two different redox states. Surprisingly, oxidation of the ruthenium redox-active metal coupling unit (MCU), which introduces an additional spin unit on the carbon-rich part, leads to weaker magnetic interactions. In contrast, in the simpler parent complexes bearing only one paramagnetic metal unit [Ph-C≡C-Ru(dppe)2-C≡C-bipyCu(hfac)2], one-electron oxidation of the ruthenium bis(acetylide) unit generates an interaction between the Cu and Ru spin carriers of magnitude comparable to that observed between the two far apart Cu ions in the above corresponding neutral trimetallic system. Evaluation and rationalization of this coupling with theoretical tools are in rational agreement with experiments for such complex systems.

Highly Axial Magnetic Anisotropy in a N3 O5 Dysprosium(III) Coordination Environment Generated by a Merocyanine Ligand.

A spiropyran-based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N3 O5 coordination sphere. The air-stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor.

Modulation of Eu(III) and Yb(III) Luminescence Using a DTE Photochromic Ligand.

In this work, we show that a dithienylethene (DTE) modified dipicolinic amide ligand can be a versatile tool to modulate Eu(III) and Yb(III) luminescence using light as an external stimulus. The nature of the modulation depends on the lanthanide emitter: with the europium ion, the DTE ligand quenches the red luminescence upon ring closure, whereas with the ytterbium ion, ring closure can be used to turn on the luminescence in the NIR range.

Fast Electron Transfer Exchange at Self-Assembled Monolayers of Organometallic Ruthenium(II) σ-Arylacetylide Complexes.

A new series of ruthenium organometallic carbon-rich complexes, exhibiting fast electron transfer kinetics combined to a low oxidation potential, was synthesized for self-assembled monolayer (SAM) formation on gold surfaces. The molecules consist of highly conjugated ruthenium(II) mono(σ-arylacetylide) or bis(σ-arylacetylide) complexes functionalized with different bridge units with specific (protected) anchoring groups that possess high affinity for gold, such as thiol, carbodithioate, and isocyanide. Single component and mixed SAMs were prepared and fully characterized by wettability studies, infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and electrochemical analyses. By applying the Laviron's formalism, fast electron transfer kinetics (≈10(4) s(-1)) were found at the derived self-assemblies while no significant effect could have been evidenced with variation of the bridging unit and of the anchoring moiety. Interestingly, a hexyl aliphatic spacer in the bridging unit with a thiol group and dilution with suitable nonelectroactive thiols lead to better SAM organization and packing, in comparison with undiluted complexes with shorter spacers. Such features make these compounds suitable alternatives to the widely used ferrocene center as redox-active building blocks for reversible charge storage devices.

Ruthenium Carbon-Rich Complexes as Redox Switchable Metal Coupling Units.

With the help of EPR spectroscopy, we show that the diamagnetic [Ru(dppe)2(-C≡C-R)2] system sets up a magnetic coupling between two organic radicals R, i.e., two nitronyl nitroxide or two verdazyl units, which is stronger than that of related platinum organometallic systems. Surprisingly, further oxidation of the ruthenium redox-active metal coupling unit (MCU), which introduces an additional spin unit on the carbon-rich part, leads to the switching off of this interaction. On the contrary, in simpler complexes bearing only one of the organic radical ligands [C6H5-C≡C-Ru(dppe)2-C≡C-R], one-electron oxidation of the transition metal unit generates an interaction between the two spin carriers of comparable magnitude to that observed in the above corresponding neutral systems.

Redox modulation of magnetic slow relaxation in a 4f-based single-molecule magnet with a 4d carbon-rich ligand.

A ruthenium carbon-rich-based ligand that brings redox reversibility to a dysprosium-based single-molecule magnet is reported. Long-distance perturbation of the 4f ion is achieved upon oxidation, resulting in an overall enhancement of the magnetic slow relaxation.

Diarylethene-containing carbon-rich ruthenium organometallics: tuning of electrochromism.

The association of a dithienylethene (DTE) system with ruthenium carbon-rich systems allows reaching sophisticated and efficient light- and electro-triggered multifunctional switches R-[Ru]-C≡C-DTE-C≡C-[Ru]-R, featuring multicolor electrochromism and electrochemical cyclization at remarkably low voltage. The spin density on the DTE ligand and the energetic stabilization of the system upon oxidation could be manipulated to influence the closing event, owing to the noninnocent behavior of carbon-rich ligands in the redox processes. A combination of spectroscopic (UV-vis-NIR-IR and EPR) and electrochemical studies, with the help of quantum chemical calculations, demonstrates that one can control and get a deeper understanding of the electrochemical ring closure with a slight modification of ligands remote from the DTE unit. This electrochemical cyclization was established to occur in the second oxidized state (EEC mechanism), and the kinetic rate constant in solution was measured. Importantly, these complexes provide an unprecedented experimental means to directly probe the remarkable efficiency of electronic (spin) delocalization between two trans carbon-rich ligands through a metal atom, in full agreement with the theoretical predictions. In addition, when no cyclization occurs upon oxidation, we could achieve a redox-triggered magnetic switch.

A photochromic metallacycle with highly anisotropic Dy-F magnetic units.

A dinuclear metallacycle assembled from a bispyridyl dithienylethene linker and a highly anisotropic dysprosium based Single Molecule Magnet (SMM) shows magnetic hysteresis at 1.8 K together with photoisomerization in single crystals (SC). The impact of photoswitching on the SMM behavior is evidenced and related to the specific organization of the magnetic units.

Fully delocalized (ethynyl)(vinyl)phenylene bridged triruthenium complexes in up to five different oxidation states.

Triruthenium [(dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2)](n+) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){µ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){µ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

Electronic transport through single-molecule oligophenyl-diethynyl junctions with direct gold-carbon bonds formed at low temperature.

We report on the first systematic transport study of alkynyl-ended oligophenyl-diethynyl (OPA) single-molecule junctions with direct Au-C anchoring scheme at low temperature using the mechanically controlled break junction technique. Through quantitative statistical analysis of opening traces, conductance histograms and density functional theory studies, we identified different types of junctions, classified by their conductance and stretching behavior, for OPA molecules between Au electrodes with two to four phenyl rings. We performed inelastic electron tunneling spectroscopy and observed the excitation of Au-C vibrational modes confirming the existence of Au-C bonds at low temperature and compared the stability of molecule junctions upon mechanical stretching. Our findings reveal the huge potential for future functional molecule transport studies at low temperature using alkynyl endgroups.

Dual-gated single-molecule field-effect transistors beyond Moore's law.

As conventional silicon-based transistors are fast approaching the physical limit, it is essential to seek alternative candidates, which should be compatible with or even replace microelectronics in the future. Here, we report a robust solid-state single-molecule field-effect transistor architecture using graphene source/drain electrodes and a metal back-gate electrode. The transistor is constructed by a single dinuclear ruthenium-diarylethene (Ru-DAE) complex, acting as the conducting channel, connecting covalently with nanogapped graphene electrodes, providing field-effect behaviors with a maximum on/off ratio exceeding three orders of magnitude. Use of ultrathin high-k metal oxides as the dielectric layers is key in successfully achieving such a high performance. Additionally, Ru-DAE preserves its intrinsic photoisomerisation property, which enables a reversible photoswitching function. Both experimental and theoretical results demonstrate these distinct dual-gated behaviors consistently at the single-molecule level, which helps to develop the different technology for creation of practical ultraminiaturised functional electrical circuits beyond Moore's law.

d-f heterobimetallic association between ytterbium and ruthenium carbon-rich complexes: redox commutation of near-IR luminescence.

We describe how the association between an ytterbium ion and a ruthenium carbon-rich complex enables the first switching of the near-IR Yb(III) luminescence by taking advantage of the redox commutation of the carbon-rich antenna.

Multifunctional and reactive enantiopure organometallic helicenes: tuning chiroptical properties by structural variations of mono- and bis(platinahelicene)s.

Acetylacetonato-platina[6]- and -platina[7]helicenes have been prepared from 2-pyridyl-substituted benzophenanthrene ligands by following a two-step cycloplatination reaction. The photophysical properties (UV-visible absorption and emission behavior) and chiroptical properties (circular dichroism and molar rotation) of the resolved enantiomers have been measured. These metallahelicenes constitute a novel family of easily accessible helicene derivatives that exhibit large and tuneable chiroptical properties that can be rationalized theoretically and compared to the parent [6]- and [7]carbohelicenes. Furthermore, they are red phosphors at room temperature and their large chiroptical properties can be modulated by oxidation of the metal center to Pt(IV). Hetero- and homochiral diastereomeric bis(metallahelicene)s that possess a rare Pt(III)-Pt(III) scaffold bridged by benzoato ligands have also been prepared. It is shown that the heterochiral (P,M)-bis(Pt(III)-[6]helicene) 9a(1) can isomerize into the homochiral (P,P)- and (M,M)-bis(Pt(III)-[6]helicene) 9a(2). Spectral assignments and an analysis of the optical rotation of these systems were made with the help of time-dependent density functional theory. The calculations highlight the contributions of the metal centers to the chiroptical properties. For 9a(1) and 9a(2), σ-π conjugation between the helicenes and the Pt-Pt moiety may contribute strongly to the optical rotation and electronic circular dichroism.