Photoinduced processes within compact dyads based on triphenylpyridinium-functionalized bipyridyl complexes of ruthenium(II)

As an alternative to conventional charge-separation functional molecular models based on long-range ET within redox cascades, a "compact approach" has been examined. To this end, spacer elements usually inserted between main redox-active units within polyad systems have been removed, allowing extended rigidity but at the expense of enhanced intercomponent electronic communication. The molecular assemblies investigated here are of the P-(theta (1))-A type, where the theta (1) twist angle is related to the degree of conjugation between the photosensitizer (P, of {Ru(bpy)(3)}(2+) type) and the electron-acceptor (A). 4-N- and 4-N-,4'-N-(2,4,6-triphenylpyridinio)-2,2'-bipyridine ligands (A(1)-bpy and A(2)-bpy, respectively) have been synthesized to give complexes with Ru(II), 1-bpy and 2-bpy, respectively. Combined solid-state analysis (X-ray crystallography), solution studies ((1)H NMR, cyclic voltammetry) and computational structural optimization allowed verifying that theta (1) angle approaches 90 degrees within 1-bpy and 2-bpy in solution. Also, anticipated existence of strong intercomponent electronic coupling has been confirmed by investigating electronic absorption properties and electrochemical behavior of the compounds. The capability of 1-bpy and 2-bpy to undergo PET process was evaluated by carrying out their photophysical study (steady state emission and time-resolved spectroscopy at both 293 and 77 K). The conformational dependence of photoinduced processes within P-(theta (1))-A systems has been established by comparing the photophysical properties of 1-bpy (and 2-bpy) with those of an affiliated species reported in the literature, 1-phen. A complementary theoretical analysis (DFT) of the change of spin density distribution within model [1-bpy(theta (1))](-) mono-reduced species as a function of theta (1) has been undertaken and the possibility of conformationally switching emission properties of P was derived.     

Monolayer Rectifiers

Molecular-scale electronics has now been enriched by the discovery that molecules, studied singly by scanning tunneling spectroscopy, or a large array of those molecules, studied in parallel as a Langmuir-Blodgett monolayer between metal electrodes, exhibit rectification, i.e., an asymmetric current as a function of applied voltage.This asymmetry can come, first, from work function differences between two dissimilar metals or the metal-molecule interfaces (Schottky barriers), second from an asymmetric placement of the chromophore between the two metal electrodes, and third, from an asymmetry of the molecular orbitals of the molecule.This third, electronic origin of rectification, first proposed by Aviram and Ratner in 1974, and confirmed in the work reported here, gives us hope that, not too many years from now, molecules can form the basis of ultra-small yet ultra-fast electronic devices and integrated circuits.     

Controllable donor-acceptor neutral [2]rotaxanes

In pursuit of a neutral bistable [2]rotaxane made up of two tetraarylmethane stoppers--both carrying one isopropyl and two tert-butyl groups located at the para positions on each of three of the four aryl rings--known to permit the slippage of the pi-electron-donating 1,5-dinaphtho[38]crown-10 (1/5DNP38C10) at the thermodynamic instigation of pi-electron-accepting recognition sites, in this case, pyromellitic diimide (PmI) and 1,4,5,8-naphthalenetetracarboxylate diimide (NpI) units separated from each other along the rod section of the rotaxane's dumbbell component, and from the para positions of the fourth aryl group of the two stoppers by pentamethylene chains, a modular approach was employed in the synthesis of the dumbbell-shaped compound NpPmD, as well as of its two degenerate counterparts, one (PmPmD) which contains two PmI units and the other (NpNpD) which contains two NpI units. The bistable [2]rotaxane NpPmR, as well as its two degenerate analogues PmPmR and NpNpR, were obtained from the corresponding dumbbell-shaped compounds NpPmD, PmPmD, and NpNpD and 1/5DNP38C10 by slippage. Dynamic 1H NMR spectroscopy in CD2Cl2 revealed that shuttling of the 1/5DNP38C10 ring occurs in NpNpR and PmPmR, with activation barriers of 277 K of 14.0 and 10.9 kcal mol(-1), respectively, reflecting a much more pronounced donor-acceptor stabilizing interaction involving the NpI units over the PmI ones. The photophysical and electrochemical properties of the three neutral [2]rotaxanes and their dumbbell-shaped precursors have also been investigated in CH2Cl2. Interactions between 1/5DNP38C10 and PmI and NpI units located within the rod section of the dumbbell components of the [2]rotaxane give rise to the appearance of charge-transfer bands, the energies of which correlate with the electron-accepting properties of the two diimide moieties. Comparison between the positions of the visible absorption bands in the three [2]rotaxanes shows that, in NpPmR, the major translational isomer is the one in which 1/5DNP38C10 encircles the NpI unit. Correlations of the reduction potentials for all the compounds studied confirm that, in this non-degenerate [2]rotaxane, one of the translational isomers predominates. Furthermore, after deactivation of the NpI unit by one-electron reduction, the 1/5DNP38C10 macrocycle moves to the PmI unit. Li+ ions have been found to strengthen the interaction between the electron-donating crown ether and the electron-accepting diimide units, particularly the PmI one. Titration experiments show that two Li+ ions are involved in the strengthening of the donor-acceptor interaction. Addition of Li+ ions to NpPmR induces the 1/5DNP38C10 macrocycle to move from the NpI to the PmI unit. The Li+-ion-promoted switching of NpPmR in a 4:1 mixture of CD2Cl2 and CD3COCD3 has also been shown by 1H NMR spectroscopy to involve the mechanical movement of the 1/5DNP38C10 macrocycle from the NpI to the PmI unit, a process that can be reversed by adding an excess of [12]crown-4 to sequester the Li+ ions.     

Molecular reactors and machines: applications, potential, and limitations

Molecular reactors are miniature vessels for the assembly of reactants at the molecular level, in order to change the nature of chemical transformations. It seems probable that those that will find most immediate applications are those that change product ratios or give products which would not readily form in the absence of the reactors, and thereby afford easy access to materials that are otherwise difficult to obtain. Molecular machines consist of interrelated parts with separate functions and perform some kind of work, at the molecular level. Practical examples are likely to be relatively uncomplicated and not based on individual functions of single-molecule devices. Instead they will probably rely on extensive redundancy of the molecular components and their interactions and reactions, as well as of the machines themselves.     

Mechanism of Macroscopic Motion of Oleate Helical Assemblies: Cooperative Deprotonation of Carboxyl Groups Triggered by Photoisomerization of Azobenzene Derivatives

Macroscopic and spatially ordered motions of self‐assemblies composed of oleic acid and a small amount of an azobenzene derivative, induced by azobenzene photoisomerization, was previously reported. However, the mechanism of the generation of submillimeter‐scale motions by the nanosized structural transition of azobenzene was not clarified. Herein, an underlying mechanism of the motions is proposed in which deprotonation of carboxyl groups in cooperation with azobenzene photoisomerization causes a morphological transition of the self‐assembly, which in turn results in macroscopic forceful dynamics. The photoinduced deprotonation was investigated by potentiometric pH titration and FTIR spectroscopy. The concept of hierarchical molecular interaction generating macroscale function is expected to promote the next stage of supramolecular chemistry.     

Partial Hydrolysis of Cyanide Coordination Polymers Induced by a Pillar Ligand with Optimized Electrochemical Kinetics for Rechargeable Alkaline Batteries

Coordination polymers are promising cathode materials for rechargeable alkaline batteries. Therefore, the precise modulation of these cathodes by chemical structure and in-depth structure transform study is necessary. Here, two model coordination polymer battery cathodes were designed to demonstrate the dynamic structure–performance relationship. We studied the electrochemical performance of two kinds of nickel-based coordination polymer, comprising a planar 2D cyanide-bridged network and a 3D cyanide-bridged network pillared by pyrazine molecules. The 2D coordination polymer showed serious voltage degradation with poor rate capability, whereas the 3D coordination polymer exhibited stable voltage output coupled with high rate at various current densities. The investigation revealed the underlining relationship of plateau voltage degradation and hydrolysis process of electrodes. It was revealed that the pyrazine pillar molecules in the 3D coordination polymer could suppress the hydrolysis and lead to the in situ formation of partially hydrolyzed structure with excellent electrochemical kinetics; this exhibited obvious smaller peak separation (27 mV compared with 149 mV) and hence an almost twofold increase in capacity retention (31.9 to 50.0 %) and energy density retention (18.2 to 35.9 %) at 10 A g⁻¹.     

Isoregic Thienylene‐Phenylene Polymers: The Effects of Structural Variation and Application to Photovoltaic Devices

Isoregic conjugated polymers composed of thiophene and dialkoxybenzene units were designed to harvest incident light in the mid‐visible energy range (band gap of 2.1 eV). Poly(1,4‐bis(2‐thienyl)‐2,5‐diheptoxybenzene) (PBTB(OC₇H₁₅)₂) and poly(1,4‐bis(2‐thienyl)‐2,5‐didodecyloxybenzene) (PBTB(OC₁₂H₂₅)₂) have shown significant photovoltaic performance as an electron donor when used in tandem with the electron acceptor [6, 6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) in bulk hetero‐junction photovoltaic devices. Photovoltaic devices incorporating PBTB(OC₇H₁₅)₂ and PCBM have shown AM1.5 efficiencies of ～0.6% with a short circuit current density of 2.5 mA/cm², an open circuit voltage of 0.74 V, and a fill factor of 0.32. Incident Photon‐to‐Current Efficiency (IPCE) of the device was found to be ca. 16% at 410 nm. In order to examine the relationship between the molecular structure of the polymers and their electronic energy levels, and to correlate this with photovoltaic performance, optoelectronic and electrochemical results are discussed in relation to the I‐V characteristics of the devices. Additionally, a computer‐aided simulation is used to gain further insight into the effect of polymer structure on the energetic relationships in the bulk heterojunction devices.     

A Resettable Keypad Lock with Visible Readout Based on Closed Bipolar Electrochemistry and Electrochromic Poly(3‐methylthiophene) Films

A closed bipolar electrode (BPE) system was developed with electrochromic poly(3‐methylthiophene) (PMT) films electropolymerized on the ITO/rGO electrode as one pole of BPE in the reporting reservoir and the bare ITO electrode as another pole of BPE in the analyte reservoir, in which rGO represents reduced graphene oxide. Under a suitable driving voltage (V_tot), the electrochemical reduction/oxidation of electroactive probes, such as H₂O₂/glutathione (Glu), in the analyte reservoir could induce the reversible color change of PMT films in the reporting reservoir between blue and red. Based on this, a keypad lock with H₂O₂, Glu, and V_tot=?3.0 V as the three inputs and the color change of PMT films as the visible output was established. This system was easily operated and did not need to synthesize the complex compounds or DNA molecules. The security system was easy to reset and could be used repeatedly.     

Organic Positive Materials for Magnesium Batteries: A Review

Magnesium batteries, like lithium-ion batteries, with higher abundance and similar efficiency, have drawn great interest for large-scale applications such as electric vehicles, grid energy storage and many more. On the other hand, the use of organic electrode materials allows high energy-performance, metal-free, environmentally friendly, versatile, lightweight, and economically efficient magnesium storage devices. In particular, the structural diversity and the simple activity of organic molecules make redox properties, and hence battery efficiency, easy to monitor. While organic magnesium batteries still in their infancy, this field becomes more and more promising because significant results were reported. To summarize the achievements in studies on organic cathodes for magnesium systems, their synthesis is discussed, combined with electrode design to provide the basis for controlling the electrochemical properties. Moreover, the techniques to synthesize organic materials with high-yield are mentioned. Finally, potential problems and prospects are explored to further improve organic cathodes.