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TiO2 photoelectrodes modified with organic dyes with pyridine anchoring groups are prepared, which are used as photoanodes of dye-sensitized photoelectrochemical cells for efficient water reduction with high photocurrent density and stability in aqueous solutions. Vigorous H2 generation with a production rate of around 250 μmol h−1 is realized with a photoanode of an active area of 5 × 5 cm2. [ABSTRACT FROM AUTHOR]

Although perovskite solar cells (PSCs) have achieved remarkably high efficiency (25.7%), their long-term stability still needs to be addressed for commercial applications. As an important part of PSCs, the hole-transporting layer (HTL) plays a crucial role in the overall device performance. Zinc porphyrin (ZnP) has excellent thermal/chemical stability, which is beneficial for enhancing the stability of PSCs when it is used as the HTL. In addition, the strong hydrophobicity of the electropolymerized film surface is believed to suppress heterogeneous nucleation and thus improve the quality of the resulting perovskite film. Herein, we have utilized the electropolymerized ZnP (PZnP) to fabricate the dopant-free HTL without annealing. The MAPb(CI0.05I0.95)3 PSCs based on PZnP presented a record-high power conversion efficiency (PCE) of 19.75%, which was significantly improved as compared to the previously reported best result of 16.7% with electropolymerized HTL. The unencapsulated PSCs sustained around 70% of the initial efficiency after thermal aging at 85 °C for 480 h, while the PTAA-based PSCs showed a 78% decrease in the initial PCE under the same conditions. Moreover, the long-term stability of the electropolymerized film-based PSCs was exceptional, retaining about 96% of the initial performance over 5000 h. The electropolymerization strategy provides an effective approach for developing cost-effective dopant-free HTL for thermally stable and efficient PSCs. [ABSTRACT FROM AUTHOR]

Well-defined luminescent micro/nanostructures are important building blocks for miniaturized photonic devices. In this work, a simple method is employed to prepare organic microspheres and crystalline microrods with circularly polarized luminescence (CPL) properties. The in situ protonation and co-assembly of a series of pyridine-functionalized chromophores and a chiral binaphthol phosphoric acid give rise to blue-to-yellow emissive amorphous microspheres and green- and yellow-emissive crystalline microrods with good fluorescence quantum yields (9.6–64.6%). The luminescence dissymmetry factors (glum) of microrods (∼10−3) are found to be one order of magnitude larger than those of microspheres. These microstructures and related materials are further characterized by fluorescence microscopy, scanning electron microscopy, single-crystal and powder X-ray diffraction, and Fourier transform-infrared spectroscopy analyses. The well-defined morphologies and promising luminescence properties of these microstructures make them potentially useful for chiral photonic applications. [ABSTRACT FROM AUTHOR]

Electrochemiluminescence (ECL) of crystalline materials has recently attracted increasing attention due to their unique characteristics and applications, such as crystallization-induced emission, active waveguiding, and biosensing. Tris(2,2′-bipyridine)ruthenium(II), [Ru(bpy)3]2+, a classical metal–organic complex for ECL studies, has been fully investigated in solution as well as its derivatives. However, the dependence of ECL properties on the molecular structure and crystal morphology of these complexes has not been illustrated, partially due to the difficulty in the controlled crystal growth. Here, we adopt a facile molecular engineering strategy to obtain microcrystals of [Ru(bpy)3]2+ derivatives with well-defined morphology (rods, wires, or polyhedrons) and varied phosphorescence emission colors (yellow, orange, and red) by simply changing the position and number of methyl substituents on the bipyridine ligands. The packing modes of molecules influenced by methyl groups play a vital role in crystal growth based on attachment energy analysis. The obtained microcrystals could act as ECL luminophores when modified on glassy carbon electrode surfaces. Those with one-dimensional (1D) morphology generally show superior ECL efficiency and stability to three-dimensional (3D) shaped microcrystals. ECL biosensors made of stable 1D microcrystals show reliable and sensitive responses to hydroxyproline, demonstrating their capacity in recyclable detections. This work demonstrates the great potential of molecular engineering in controlling the morphology, emission colors, and ECL properties of molecular crystals, paving the way for the development of high-performance ECL biosensing and optoelectronic devices. [ABSTRACT FROM AUTHOR]

Three cyclometalated diruthenium complexes bridged by 3,3′,5,5′-tetrakis(benzimidazol-2-yl)biphenyl (H-tbibp) and capped with different terminal ligands have been synthesized and examined. In addition, two monoruthenium complexes with H-tbibp have been prepared for the purpose of comparison studies. The degree of Ru–Ru electronic coupling of these diruthenium complexes has been investigated by electrochemical and intervalence charge-transfer (IVCT) analyses. These results suggest that when the same or similar terminal ligands are used, the strength of H-tbibp in mediating the Ru–Ru coupling is enhanced with respect to that of the previously reported bridging ligand 3,3′,5,5′-tetrakis(N-methylbenzimidazol-2-yl)biphenyl, but it is slightly inferior to that of the classical bridging ligand 3,3′,5,5′-tetrakis(pyrid-2-yl)biphenyl. This trend is also supported by CNS analyses based on the hole-superexchange mechanism. In addition, DFT calculations have been performed to probe the spin density distributions of the singly-oxidized diruthenium complexes with H-tbibp and TDDFT calculations are used to reproduce the IVCT transitions. [ABSTRACT FROM AUTHOR]

Lithium-ion batteries (LIBs) have been demonstrated as one of the most promising energy storage devices for applications in electric vehicles, smart grids, large-scale energy storage systems, and portable electronics. Compared with traditional inorganic compounds that often cause various environmental problems, organic electrode materials possess many advantages, such as the diversity of molecular structures, feasibility of subjective design, light weight, low cost, high theoretical capacity, and eco-friendliness, making them very promising in the application of energy-related devices. Among all organic materials used as electrodes for LIBs, organic carbonyl-based polymers with multi-electron reaction centers, high theoretical capacity, reaction reversibility, rapid redox kinetics, and the inhibition of electrolyte dissolution have recently become hot topics. In this review, we summarize the recent progress in the design, synthesis, and application of carbonyl-based polymers for LIBs. In addition, the advantages/disadvantages of individual materials are also discussed. [ABSTRACT FROM AUTHOR]

A dual-emissive tris-heteroleptic ruthenium complex is designed, synthesized and applied for the ratiometric photoluminescent detection of amyloid-β (Aβ) aggregation in both steady and transient states. The Aβ aggregation is supported by transmission electron microscopy and confocal laser scanning microscopy analysis. In addition, molecular docking calculations have been performed to gain insights into the interaction mode between the ruthenium complex and Aβ fibrils. [ABSTRACT FROM AUTHOR]

A new small molecular hole-transporting material, 1,3,6,8-tetrakis[N-(p-methoxyphenyl)-N′-(9,9′-dimethyl-9H-fluoren-2-yl)-amino]pyrene (TFAP) was synthesized and applied in CH3NH3PbI3-perovskite solar cells. A best power conversion efficiency of 19.7% with a photovoltage of 1.11 V has been achieved. [ABSTRACT FROM AUTHOR]

Sb-Doped nanocrystalline SnO2 (SnO2:Sb) thin films functionalized with cyclometalated ruthenium complexes 1 or 2 on FTO conductive glasses have been prepared and characterized. These complexes contain a redox-active amine unit separated from the ruthenium ion by a phenyl or biphenyl linker, respectively, to modify the absorption wavelengths at different redox states. Near-infrared electrochromism of both films has been examined by oxidative spectroelectrochemical measurements and double-potential-step chronoamperometry. A contrast ratio (ΔT%) of 33% at 1070 nm and 63% at 696 nm has been achieved for the SnO2:Sb/1 film in two stepwise oxidation processes, respectively. The other film with complex 2 shows two-step electrochromism at 1310 and 806 nm with ΔT% of 36% and 76%, respectively. The response time of electrochromic switching is around a few seconds. Taking advantage of the good contrast ratio, the rapid response, and the long retention time of each oxidation state, these films have been successfully used to demonstrate surface-confined flip-flop memory functions with a high ON/OFF ratio. [ABSTRACT FROM AUTHOR]

Treatment of tetrakis(dimethylamino)diboron (B2(NMe2)4) with 1,4-bis(2-(triisopropylsilyl)ethynyl)naphthalene-2,3-diamine (1) generated a large NBBN polycyclic compound 1,1-B2{2,3-(NH)2-1,4-(iPr3SiC2)2C10H4} (2). The X-ray structure analysis reveals that 2 has a twisted structure (dihedral angle ≈ 21.75°) with a rather short B–B bond (1.667(9) Å). Theoretical calculations on 1,1-B2 isomer 2 and its counterpart 1,2-B2 isomer 3 have been conducted to understand their frontier orbital energy levels. Compound 2 shows strong emission with a high quantum yield of 0.52, despite the presence of many unbeneficial non-radiative behaviors such as the vibration of the TIPS groups and the rotation of the B–B single bond. [ABSTRACT FROM AUTHOR]

As a pump for extracting carriers from the absorber to the cathode, hole transporting materials (HTMs) play indispensable roles in promoting the power conversion efficiencies (PCE) of perovskite solar cells (PSCs). In this context, we present two simple HTMs using 2,2′-(1,2-phenylene) bisthiophene or naphtho[1,2-b:4,3-b′]dithiophene as a π-bridge to link two electron-donor units (4′,4′′-dimethoxytriphenylamine): PBT and NDT. Their frontier molecular orbital energies match well with those of perovskites as is consistent with the DFT calculation results. The PCE measured under mimetic solar illumination (AM 1.5, 100 mW cm−2) increases from 13.6% (PBT) to 18.8% (NDT), which surpass that of the spiro-OMeTAD (18.1%) reference. The modified annulated core in NDT makes it perform better in photovoltaic conversion than PBT. The reason for this is discussed from aspects of hole mobility, charge collection probability (Pc) and recombination kinetics. [ABSTRACT FROM AUTHOR]

Two new hole transporting materials (HTMs) based on triphenylamine and carbazole core moieties are designed and applied in planar perovskite solar cells. 18.2% power conversion efficiency (PCE) has been achieved, and 84% of the initial performance can be retained after 50 days. [ABSTRACT FROM AUTHOR]

A polypyridyl monoruthenium complex with a dangling coordination site shows dual fluorescence/phosphorescence emissions at room temperature. The emission properties can be modulated by multiple stimuli including solvents, O2, and metal ions. [ABSTRACT FROM AUTHOR]

Four bridged cyclometalated diruthenium systems are highlighted in this Frontier article, including strongly-coupled diruthenium complexes with a short phen-1,4-diyl or a planar pyren-2,7-diyl bridge, redox asymmetric diruthenium complexes characterized by different terminal ligands on the two ends, diruthenium complexes with a urea bridge that allows modulating the degree of electronic coupling, and those with a redox-active amine bridge with varying electronic structures. These complexes posess redox couples with low potentials and intense intervalence charge transfer absorptions in the near-infrared region in the one-electron-oxidized mixed-valent state. They are appealing not only for providing a platform for fundamental electron transfer studies but also as molecular materials with multi-stage redox switching properties. [ABSTRACT FROM AUTHOR]

The ITO/active material/Au sandwiched devices of a cobalt(ii) bis-terpyridine complex decorated with two triphenylamine motifs display appealing flash-type resistive switching with a large ON/OFF ratio (＞103) and low operating voltages (＜±3 V). In contrast, devices with the triphenylamine-appended terpyridine ligand show WORM-type memory behaviour. [ABSTRACT FROM AUTHOR]

For the purpose of developing multicolor emissive molecular materials, a U-shaped diplatinum molecular switch 1 with an N,N-dimethylurea bridge was prepared. Three forms of single crystals of 1 with yellow (1A), orange (1B), or red (1C) emission were obtained. X-ray analysis shows that the two constituent [Pt(NCN)] units can have an open (1A and 1C) or closed (1B) conformation with different modes of crystal packing. In particular, intermolecular Pt–Pt interaction is evident for 1C with a short Pt–Pt distance of 3.226 Å. The interconversion among these crystals was triggered by external conditions, with the aid of an additional form of crystal 1D. The deep-red emissive crystal 1C exhibits excellent photophysical properties with λmax,emi of 650 nm, Φ of 36%, and τ of 846 ns. Spectroscopic analysis supports the hypothesis that compound 1 has a dominant open conformation in CHCl3 and a closed conformation in MeOH solution. The conformational switching and the degree of intermolecular interaction with tunable emission colors can be regulated by solvent composition. [ABSTRACT FROM AUTHOR]

A combined study of electrochemical measurements, intervalence charge transfer analysis, and DFT calculations suggests that the degree of urea-mediated electronic coupling between two cyclometalated ruthenium sites is enhanced by the coordination of urea with Br− or Cl−via hydrogen bonding. In contrast, the redox waves of the diruthenium complex become highly irreversible in the presence of relatively strong basic anions such as H2PO4−, F−, or OAc−. This work demonstrates that the anion–urea interaction can be employed to regulate the electronic coupling and electron transfer between redox-active sites, suggesting the potential applications of the urea-functionalized diruthenium complex in anion sensing and stimuli-responsive molecular electronics. [ABSTRACT FROM AUTHOR]

In response to the application of low electrochemical potentials, ruthenium-tris(bipyridine) complexes decorated with multiple electron-rich and redox-active amine substituents show reversible absorption and emission spectral changes in the deep-red to NIR region. The number of amine substituents strongly affects the electrochemical and spectroscopic properties and the spin density distributions of the complex in the one-electron-oxidized state. [ABSTRACT FROM AUTHOR]

A series of C^N ligands with donor–acceptor (D–A) frameworks, i.e. TPA-BTPy, TPA-BTPy-Fl and Fl(TPA-BTPy)2, as well as their mono- and di-nuclear platinum(ii) complexes of (TPA-BTPy)Pt(pic), (TPA-BTPy-Fl)Pt(pic) and [Fl(TPA-BTPy)2]Pt2(pic)2 are respectively designed and synthesized, in which triphenylamine (TPA) and fluorene (Fl) are used as the D units, 4-(pyrid-2-yl)benzothiadiazole (BTPy) as the A unit, and the picolinate anion (pic) as the auxiliary ligand. Their thermal, photophysical and electrochemical characteristics were investigated. Compared to mono-nuclear platinum complexes and their free ligands, this dinuclear one of [Fl(TPA-BTPy)2]Pt2(pic)2 shows an obvious interaction from the platinum atom to ligand and dual emission peaks at 828 and 601 nm in thin films. Upon oxidation with antimony pentachloride in dichloromethane, charge transfer transitions between the platinum and ligand are observed for the three complexes. The single-emissive-layer polymer light-emitting devices doped with [Fl(TPA-BTPy)2]Pt2(pic)2 display a strong electroluminescence with dual emission peaks at 780 and 600 nm at a dopant concentration over 4 wt%. A maximum external quantum efficiency of 0.02% with a radiance of 59 μW cm−2 is obtained in the device at 30 wt% dopant concentration. This work indicates that the use of an extended D–A-type ligand is an effective strategy to achieve NIR emission for platinum complexes in PLEDs. [ABSTRACT FROM AUTHOR]

Hybrid films of functional molecules and metal nanoparticles have been considered to be novel photo-functional devices. Here we have successfully constructed hybrid films of silver nanoparticles and ruthenium polypyridine derivatives on substrates. In order to hybridise them on a surface, a self-assembled monolayer method via chemical bond formation and electro-reductive polymerisation (thick layers) via physical attachment have been employed. These methods have the advantage of convenient and reproducible fabrication of complicated hybrid films. Furthermore, it has been clarified that these hybrid films show unique photo-functional behaviours, such as enhanced photocurrent generation. [ABSTRACT FROM AUTHOR]

Through Ru(ii)-catalyzed C–H bond activation, a methodology for the synthesis of 2- or 2,7-functionalized pyrene derivatives has been developed using the substrate 1-(pyrid-2-yl)pyrene or 1,6-di(pyrid-2-yl)pyrene. [ABSTRACT FROM AUTHOR]

Four bis-tridentate ruthenium complexes with 5,5′′-divinyl-4′-tolyl-2,2′:6′,2′′-terpyridine (dvtpy) have been synthesized. Among them, 3(PF6) ([(dvtpy)Ru(Mebib)](PF6)) and 4(PF6) ([(dvtpy)Ru(dpb)](PF6)) are cyclometalated, and 5(PF6)2 ([(dvtpy)Ru(Mebip)](PF6)2) and 6(PF6)2 ([(dvtpy)Ru(tpy)](PF6)2) are noncyclometalated, where Mebib is 2-deprotonated-1,3-bis(N-methylbenzimidazolyl)benzene, dpb is 2-deprotonated-1,3-di(2-pyridyl)benzene, Mebip is 2,6-bis(N-methylbenzimidazolyl)pyridine, and tpy is 2,2′:6′,2′′-terpyridine, respectively. Reductive electropolymerization of these complexes and copolymerization of 4(PF6) and 5(PF6)2 proceeded smoothly, both on glassy carbon and ITO glass electrodes, to afford stable metallopolymeric films with well-defined redox processes. On the basis of the monomer structures, electrochemical properties, and polymerization mechanism, the polymer chains of these materials are supposed to be composed of organic frameworks with the metal ions laterally chelated to the main backbones. The polymeric films on ITO surfaces display promising electrochromism in the visible region with good reversibility and moderate contrast ratio. Besides, the apparent diffusion constants of films of 3(PF6)–6(PF6)2 were measured by potential step chronoamperometry and the typical surface morphology of poly-5(PF6)2/ITO film was studied using SEM. [ABSTRACT FROM AUTHOR]

In situ one-pot rapid layer-by-layer assembly of polymeric films as an active layer of a photoactive device via alternation of reductive and oxidative electropolymerization has been demonstrated. This novel fabrication without moving or changing experimental gears would be a powerful strategy to develop automated layer-by-layer machines. [ABSTRACT FROM AUTHOR]

TiO 2 photoelectrodes modified with organic dyes with pyridine anchoring groups are prepared, which are used as photoanodes of dye-sensitized photoelectrochemical cells for efficient water reduction with high photocurrent density and stability in aqueous solutions. Vigorous H 2 generation with a production rate of around 250 μmol h -1 is realized with a photoanode of an active area of 5 × 5 cm 2 .

Three cyclometalated diruthenium complexes bridged by 3,3',5,5'-tetrakis(benzimidazol-2-yl)biphenyl (H-tbibp) and capped with different terminal ligands have been synthesized and examined. In addition, two monoruthenium complexes with H-tbibp have been prepared for the purpose of comparison studies. The degree of Ru-Ru electronic coupling of these diruthenium complexes has been investigated by electrochemical and intervalence charge-transfer (IVCT) analyses. These results suggest that when the same or similar terminal ligands are used, the strength of H-tbibp in mediating the Ru-Ru coupling is enhanced with respect to that of the previously reported bridging ligand 3,3',5,5'-tetrakis(N-methylbenzimidazol-2-yl)biphenyl, but it is slightly inferior to that of the classical bridging ligand 3,3',5,5'-tetrakis(pyrid-2-yl)biphenyl. This trend is also supported by CNS analyses based on the hole-superexchange mechanism. In addition, DFT calculations have been performed to probe the spin density distributions of the singly-oxidized diruthenium complexes with H-tbibp and TDDFT calculations are used to reproduce the IVCT transitions.

Sb-Doped nanocrystalline SnO2 (SnO2:Sb) thin films functionalized with cyclometalated ruthenium complexes 1 or 2 on FTO conductive glasses have been prepared and characterized. These complexes contain a redox-active amine unit separated from the ruthenium ion by a phenyl or biphenyl linker, respectively, to modify the absorption wavelengths at different redox states. Near-infrared electrochromism of both films has been examined by oxidative spectroelectrochemical measurements and double-potential-step chronoamperometry. A contrast ratio (ΔT%) of 33% at 1070 nm and 63% at 696 nm has been achieved for the SnO2:Sb/1 film in two stepwise oxidation processes, respectively. The other film with complex 2 shows two-step electrochromism at 1310 and 806 nm with ΔT% of 36% and 76%, respectively. The response time of electrochromic switching is around a few seconds. Taking advantage of the good contrast ratio, the rapid response, and the long retention time of each oxidation state, these films have been successfully used to demonstrate surface-confined flip-flop memory functions with a high ON/OFF ratio.

Four bridged cyclometalated diruthenium systems are highlighted in this Frontier article, including strongly-coupled diruthenium complexes with a short phen-1,4-diyl or a planar pyren-2,7-diyl bridge, redox asymmetric diruthenium complexes characterized by different terminal ligands on the two ends, diruthenium complexes with a urea bridge that allows modulating the degree of electronic coupling, and those with a redox-active amine bridge with varying electronic structures. These complexes posess redox couples with low potentials and intense intervalence charge transfer absorptions in the near-infrared region in the one-electron-oxidized mixed-valent state. They are appealing not only for providing a platform for fundamental electron transfer studies but also as molecular materials with multi-stage redox switching properties.

A polypyridyl monoruthenium complex with a dangling coordination site shows dual fluorescence/phosphorescence emissions at room temperature. The emission properties can be modulated by multiple stimuli including solvents, O 2 , and metal ions.

In response to the application of low electrochemical potentials, ruthenium-tris(bipyridine) complexes decorated with multiple electron-rich and redox-active amine substituents show reversible absorption and emission spectral changes in the deep-red to NIR region. The number of amine substituents strongly affects the electrochemical and spectroscopic properties and the spin density distributions of the complex in the one-electron-oxidized state.

A series of C^N ligands with donor-acceptor (D-A) frameworks, i.e. TPA-BTPy, TPA-BTPy-Fl and Fl(TPA-BTPy)2, as well as their mono- and di-nuclear platinum(II) complexes of (TPA-BTPy)Pt(pic), (TPA-BTPy-Fl)Pt(pic) and [Fl(TPA-BTPy)2]Pt2(pic)2 are respectively designed and synthesized, in which triphenylamine (TPA) and fluorene (Fl) are used as the D units, 4-(pyrid-2-yl)benzothiadiazole (BTPy) as the A unit, and the picolinate anion (pic) as the auxiliary ligand. Their thermal, photophysical and electrochemical characteristics were investigated. Compared to mono-nuclear platinum complexes and their free ligands, this dinuclear one of [Fl(TPA-BTPy)2]Pt2(pic)2 shows an obvious interaction from the platinum atom to ligand and dual emission peaks at 828 and 601 nm in thin films. Upon oxidation with antimony pentachloride in dichloromethane, charge transfer transitions between the platinum and ligand are observed for the three complexes. The single-emissive-layer polymer light-emitting devices doped with [Fl(TPA-BTPy)2]Pt2(pic)2 display a strong electroluminescence with dual emission peaks at 780 and 600 nm at a dopant concentration over 4 wt%. A maximum external quantum efficiency of 0.02% with a radiance of 59 μW cm(-2) is obtained in the device at 30 wt% dopant concentration. This work indicates that the use of an extended D-A-type ligand is an effective strategy to achieve NIR emission for platinum complexes in PLEDs.

Hybrid films of functional molecules and metal nanoparticles have been considered to be novel photo-functional devices. Here we have successfully constructed hybrid films of silver nanoparticles and ruthenium polypyridine derivatives on substrates. In order to hybridise them on a surface, a self-assembled monolayer method via chemical bond formation and electro-reductive polymerisation (thick layers) via physical attachment have been employed. These methods have the advantage of convenient and reproducible fabrication of complicated hybrid films. Furthermore, it has been clarified that these hybrid films show unique photo-functional behaviours, such as enhanced photocurrent generation.

Organic-inorganic mixed-valence systems with strongly-coupled triarylamine and cyclometalated osmium have been developed. They display two well-separated redox couples at low potentials. Each of the three readily accessible oxidation states can be distinguished by the absorbance at three different wavelengths.

Four bis-tridentate ruthenium complexes with 5,5′′-divinyl-4′-tolyl-2,2′:6′,2′′-terpyridine (dvtpy) have been synthesized. Among them, 3(PF6) ([(dvtpy)Ru(Mebib)](PF6)) and 4(PF6) ([(dvtpy)Ru(dpb)](PF6)) are cyclometalated, and 5(PF6)2 ([(dvtpy)Ru(Mebip)](PF6)2) and 6(PF6)2 ([(dvtpy)Ru(tpy)](PF6)2) are noncyclometalated, where Mebib is 2-deprotonated-1,3-bis(N-methylbenzimidazolyl)benzene, dpb is 2-deprotonated-1,3-di(2-pyridyl)benzene, Mebip is 2,6-bis(N-methylbenzimidazolyl)pyridine, and tpy is 2,2′:6′,2′′-terpyridine, respectively. Reductive electropolymerization of these complexes and copolymerization of 4(PF6) and 5(PF6)2 proceeded smoothly, both on glassy carbon and ITO glass electrodes, to afford stable metallopolymeric films with well-defined redox processes. On the basis of the monomer structures, electrochemical properties, and polymerization mechanism, the polymer chains of these materials are supposed to be composed of organic frameworks with the metal ions laterally chelated to the main backbones. The polymeric films on ITO surfaces display promising electrochromism in the visible region with good reversibility and moderate contrast ratio. Besides, the apparent diffusion constants of films of 3(PF6)–6(PF6)2 were measured by potential step chronoamperometry and the typical surface morphology of poly-5(PF6)2/ITO film was studied using SEM.

A cyclometalated bisruthenium complex bridged by the 2,7-bisdeprotonated form of 1,3,6,8-tetra(pyridin-2-yl)-9-butyl-9H-carbazole displays appreciably enhanced electronic coupling relative to that with the 5,5'-bisdeprotonated form of 3,3',5,5'-tetra(pyridin-2-yl)-biphenyl as the bridge.

The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4'-di-p-anisylamino-2,2':6',2''-terpyridine is presented. The Ru(II/III) redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.

A 1,4-benzene-bridged covalent hybrid of triarylamine and cyclometalated ruthenium 1(2+) was isolated as a bench-stable open-shell substance. The free spin in this complex is mainly associated with the triarylamine unit, as indicated by EPR and DFT calculations and electrochemical analysis. It exhibits an intense intervalence-charge-transfer transition around 1050 nm that is not present in 1(+) and 1(3+).