Dinuclear Metal–Organic Material for Binary Optical Recording

A diimine ligand tethered to anthracene in the 9‐position, 4′‐(9‐anthrylethyl)‐4‐methyl‐2,2′‐bipyridine (bpy‐An), was dimerized through cycloaddition photochemistry. The resultant head‐to‐tail photodimer (bpy‐PD) was used as a bridging ligand in the preparation of a new dinuclear Ru^II complex, [Ru(dmb)₂(bpy‐PD)Ru(dmb)₂]⁴⁺ (dmb = 4,4′dimethyl‐2,2′‐bipyridine). The corresponding mononuclear species containing anthracene ([Ru(dmb)₂(bpy‐An)]²⁺ was also synthesized and serves as a model compound in this study. UV photolysis (λ < 300 nm) of the strongly luminescent Ru^II dinuclear complex results in cycloreversion, generating two anthracene‐containing mononuclear species, [Ru(dmb)₂(bpy‐An)]²⁺, whose emission is largely quenched as a result of nonradiative triplet–triplet energy transfer. The photophysical and photochemical properties of the dinuclear system have been studied in CH₃CN solutions and in solid polyvinyl alcohol (PVA) thin films. The “on”–“off” luminescence switching characteristics and concomitant non‐destructive readout properties suggested that these molecules could be useful in read‐only memory (ROM) applications. In the solid state, micrometer‐sized objects were imaged using visible light, taking advantage of the luminescence contrast generated from the UV photochemical reaction. These written images were stable for at least 6 months, indicating that long‐term binary data storage is indeed feasible in these ROM metal–organic materials.     

Ultrathin Luminescent Films of Rigid Dinuclear Ruthenium(II) Trisbipyridine Complexes

Two asymmetric, luminescent, bimetallic ruthenium trisbipyridine complexes with the general formula [Ru(bpy)₃‐ph₄‐Ru(bpy) L₂](PF₆)₄ (bpy = 2,2′‐bipyridine, ph = phenyl, L = 4,4′‐di‐n‐undecyl‐2,2′‐bipyridine ( 1 ); 4,4′‐di‐non‐1‐enyl‐2,2′‐bipyridine ( 2 )) have been synthesized and characterized. The introduction of two 4,4′‐dialkyl‐2,2′‐bipyridine ligands on one of the ruthenium centers does not influence the electronic structure of the overall complexes to a large extent. Owing to the hydrophobic and hydrophilic nature of the two terminal metal complexes, the compounds 1 and 2 are expected to form Langmuir monolayers at the air/water interface. The film‐forming properties of the amphiphilic complexes have been investigated by measuring surface‐pressure–molecular‐area (π–A) isotherms and recording Brewster‐angle microscopy images. Complexes 1 and 2 were shown to form monolayer films at the air/water interface, which have subsequently been transferred to solid substrates using the Langmuir–Blodgett (LB) technique. The homogeneity of the resulting LB films has been investigated using atomic force microscopy and has been compared with that of LB films of the reference compound [Ru(bpy)₃‐ph₄‐Ru(bpy)₃](PF₆)₄ ( 3 ), which lacks the alkyl chains. The presence of the hydrocarbon chains on one side of the rigid bimetallic complexes was shown to be a prerequisite for the formation of homogeneous monolayers, as with 3 only multilayer formation was obtained. Confocal laser scanning microscopy measurements proved that the LB films of complexes 1 and 2 display a homogeneous red emission upon photoexcitation. Such important results represent the first step towards the fabrication of mono‐ or few‐molecular‐layer electroluminescent devices.     

Surface‐Confined Heterometallic Molecular Dyads: Merging the Optical and Electronic Properties of Fe,Ru, and Os Terpyridyl Complexes

Molecular assemblies of surface‐confined heterometallic molecular dyads (SURHMDs) composed of optically rich and redox‐active Fe(pytpy)₂·2PF₆ (Fe‐PT), Ru(pytpy)₂·2PF₆ (Ru‐PT) and Os(pytpy)₂·2PF₆ (Os‐PT) pytpy = 4′‐(4‐pyridyl)‐2,2′:6′,2″‐terpyridyl] complexes are fabricated via bottom‐up approach on SiO_x based solid supports. Pairing of the two different metal‐organic complexes at a single platform results in significant enlargement of the optical window (λ = 400–800 nm), which can be of interest for potential applications. The use of the Cu‐based linker ensures intramolecular electronic communication between these complexes. In addition, SURHMDs are electrochemically stable under large numbers of read‐write cycles (10³) and exhibit multiple redox states at relatively low potentials (<1.2 V). Moreover, an electrochemical input at controlled potentials creates a mixed‐valence multicomponent system.     

A Luminescence and Electrochemical Study of Photoinduced Electron Transfer within the Layers of Zirconium Phosphate

Electron donors based on Ru(bpy)₃ (bpy = 2,2′‐bipyridine) are covalently attached to the walls of γ‐ZrP and acceptor species based on viologen are arranged side by side following quite simple experimental protocols. The resulting materials are characterized by using the usual techniques and their luminescence and electrochemical properties are assessed. Strong evidence is presented of the efficient occurrence of photoinduced electron transfer in the solid state among the active species attached to the transparent inorganic matrix. The prepared materials may find applications in the clean conversion of light into useful energy.     

In Situ Grown Pristine Cobalt Sulfide as Bifunctional Photocatalyst for Hydrogen and Oxygen Evolution

Herein, transition metal chalcogenides of pristine cobalt sulfides are rationally designed to act as robust bifunctional photocatalysts for visible‐light‐driven water splitting for the first time. Through moderate solvothermal route, cobalt sulfides are synthesized in situ growth and observed by scanning electron microscope image analysis. Noteworthily, 3D hierarchical cobalt sulfides acting as bifunctional photocatalysts are implemented to catalyze the visible‐light‐driven oxygen evolution reaction and hydrogen evolution reaction. This efficient, earth‐abundant, and nonnoble water splitting catalyst for artificial photosynthesis is thoroughly analyzed by various spectroscopic techniques with the aim of investigating its photocatalytic mechanism under visible‐light illumination. The main catalyst of CoS‐2 exhibits considerable H₂ evolution rate of 1196 µmol h^?1 g^?1 and O₂ yield of 63.5%. The efficient activity is attributed to the effective electron transfer between the photosensitizer and catalyst, which is verified by transient absorption experiments. The effective electron transfer between the photosensitizer and catalyst during water oxidation is verified by the dramatic decline of [Ru(bpy)₃]³⁺ concentration in the presence of the catalyst CoS‐2. At the same time, transient absorption experiments support a rapid electron transfers from ³EY* (excited photosensitizer eosin‐Y) to the catalyst CoS‐2 for efficient hydrogen evolution.     

Functional Supramolecular Ruthenium Cyclodextrin Dyes for Nanocrystalline Solar Cells

A supramolecular complex [Ru(dcb)₂(α‐CD‐5‐bpy)]Cl₂ ( 1‐α‐CD ) (dcb = 4,4′‐dicarboxyl‐2,2′‐bipyridine, α‐CD‐5‐bpy = 6‐mono[5‐methyl(5′‐methyl‐2,2′‐bipyridyl)]‐permethylated α‐CD) (CD: cyclodextrin) based on a ruthenium tris‐bipyridyl core with an appended α‐CD cavity is designed and synthesised, in order to facilitate dye/redox couple interaction and dye regeneration in nanocrystalline TiO₂ solar cells. The luminescent complex is fully characterized and anchored on mesoporous titania electrodes showing increased power‐conversion efficiency in solid‐state dye‐sensitized solar cells using a composite polymer electrolyte. Direct comparison of the properties of the CD complex with an analogous ruthenium complex [Ru(dcb)₂(5,5′‐dmbpy)]Cl₂ ( 2 ) (5,5′‐dmbpy = 5,5′‐dimethylbipyridine) without the CD cavity reveals that the photovoltaic performance of 1‐α‐CD is enhanced by about 40 % compared to 2 . Independent studies have shown complexation of the iodide redox couple to the CD in 1‐α‐CD . These results indicate that the CD moiety is able to act as a mediator and fine tune the photoelectrode/electrolyte interface.     

Scrutinizing Design Principles toward Efficient,Long‐Term Stable Green Light‐Emitting Electrochemical Cells

Enhancing the efficiency and lifetime of light emitting electrochemical cells (LEC) is the most important challenge on the way to energy efficient lighting devices of the future. To avail this, emissive Ir(III) complexes with fluoro‐substituted cyclometallated ligands and electron donating groups (methyl and tert ‐butyl)‐substituted diimine ancillary (N^{^}N) ligands and their associated LEC devices are studied. Four different complexes of general composition [Ir(4ppy)₂(N^{^}N)][PF₆] (4Fppy = 2‐(4‐fluorophenyl)pyridine) with the N^{^}N ligand being either 2,2′‐bipyridine ( 1 ), 4.4′‐dimethyl‐2,2′‐bipyridine ( 2 ), 5.5′‐dimethyl‐2,2′‐bipyridine ( 3 ), or 4.4′‐di‐tert ‐butyl‐2,2′‐bipyridine ( 4 ) are synthesized and characterized. All complexes emit in the green region of light with emission maxima of 529–547 nm and photoluminescence quantum yields in the range of 50.6%–59.9%. LECs for electroluminescence studies are fabricated based on these complexes. The LEC based on ( 1 ) driven under pulsed current mode demonstrated the best performance, reaching a maximum luminance of 1605 cd m^?2 resulting in 16 cd A^?1 and 8.6 lm W^?1 for current and power efficiency, respectively, and device lifetime of 668 h. Compared to this, LECs based on ( 3 ) and ( 4 ) perform lower, with luminance and lifetime of 1314 cd m^?2, 45.7 h and 1193 cd m^?2, 54.9 h, respectively. Interestingly, in contrast to common belief, the fluorine content of the Ir‐iTMCs does not adversely affect the LEC performance, but rather electron donating substituents on the N^{^}N ligands are found to dramatically reduce both performance and stability of the green LECs. In light of this, design concepts for green light emitting electrochemical devices have to be reconsidered.     

Materials Surgery – Reactivity Differences of Organic Groups in Hybrids

Synergistic properties in hybrid materials can emerge if the inorganic matrix has an electronic influence on the organic constituents and vice versa. This paper describes the drastic effect of SiO₂ in periodically ordered mesoporous organosilica materials (PMOs) on ethylene groups. A sophisticated, in situ solid‐state NMR spectroscopy study showed that the ozonolysis of ethylene groups follows an entirely different mechanism than is normal for organic, molecular groups. Ultimately, this leads to the topotactic transformation of the PMO material. Only if silicon is not in the alpha position to the double bond does it became possible to establish a new method to functionalize PMOs materials: the targeted scission of the ethylene group and the creation of functionalized pockets inside the pore walls of the mesoporous solid.     

New Ruthenium Complexes Containing Oligoalkylthiophene‐Substituted 1,10‐Phenanthroline for Nanocrystalline Dye‐Sensitized Solar Cells

Two new ruthenium complexes [Ru(dcbpy)(L)(NCS)₂], where dcbpy is 4,4′‐dicarboxylic acid‐2,2′‐bipyridine and L is 3,8‐bis(4‐octylthiophen‐2‐yl)‐1,10‐phenanthroline (CYC‐P1) or 3,8‐bis(4‐octyl‐5‐(4‐octylthiophen‐2‐yl)thiophen‐2‐yl)‐1,10‐phenanthroline (CYC‐P2), are synthesized, characterized by physicochemical and semiempirical computational methods, and used as photosensitizers in nanocrystalline dye‐sensitized solar cells. It was found that the difference in light‐harvesting ability between CYC‐P1 and CYC‐P2 is associated mainly with the location of the frontier orbitals, in particular the highest occupied molecular orbital (HOMO). Increasing the conjugation length of the ancillary ligand decreases the energy of the metal‐to‐ligand charge transfer (MLCT) transition, but at the same time reduces the molar absorption coefficient, owing to the HOMO located partially on the ancillary ligand of the ruthenium complex. The incident photon‐to‐current conversion efficiency curves of the devices are consistent with the MLCT band of the complexes. Therefore, the overall efficiencies of CYC‐P1 and CYC‐P2 sensitized cells are 6.01 and 3.42 %, respectively, compared to a cis‐di(thiocyanato)‐bis(2,2′‐bipyridyl)‐4,4′‐dicarboxylate ruthenium(II)‐sensitized device, which is 7.70 % using the same device‐fabrication process and measuring parameters.     

Thiocyanate‐Free Ru(II) Sensitizers with a 4,4′‐Dicarboxyvinyl‐2,2′‐bipyridine Anchor for Dye‐Sensitized Solar Cells

A new class of thiocyanate‐free Ru(II) sensitizers with 4,4′‐dicarboxyvinyl‐2,2′‐bipyridine anchor and two trans‐oriented pyrid‐2‐yl pyrazolate (or triazolate) functional chromophores is synthesized, characterized, and evaluated in dye‐sensitized solar cells (DSCs). Despite their enhanced red response and absorptivity when compared to the parent sensitizer TFRS‐2 that possesses standard 4,4′‐dicarboxyl‐2,2′‐bipyridine anchor and shows the best conversion efficiency of η = 9.82%, the newly synthesized carboxyvinyl‐pyrazolate sensitizers, TFRS‐11 – TFRS‐13 , exhibit inferior performance characteristics in terms of short‐circuit current density (J_SC), open‐circuit voltage (V_OC), and power conversion efficiency (η), the latter being recorded to be in the range 5.60–7.62%. The reduction in device efficiencies is attributed to a combination of poor packing of these sensitizers on the TiO₂ surface and less positive ground‐state oxidation potentials, which, respectively, increase charge recombination with I₃^? in electrolytes and impede the regeneration of sensitizers by I^? anions. The latter obstacle can be circumvented in part by the replacement of the pyrazolates with triazolates, forming the TFRS‐14 sensitizer, which exhibits an improved J_SC, V_OC, and η of 16.4 mAcm^?2, 0.77 V, and 9.02%, respectively.     

Enhanced‐Light‐Harvesting Amphiphilic Ruthenium Dye for Efficient Solid‐State Dye‐Sensitized Solar Cells

A ruthenium sensitizer (coded C101, NaRu (4,4′‐bis(5‐hexylthiophen‐2‐yl)‐2,2′‐bipyridine) (4‐carboxylic acid‐4′‐caboxylate‐2,2′‐bipyridine) (NCS)₂) containing a hexylthiophene‐conjugated bipyridyl group as an ancillary ligand is presented for use in solid‐state dye‐sensitized solar cells (SSDSCs). The high molar‐extinction coefficient of this dye is advantageous compared to the widely used Z907 dye, (NaRu (4‐carboxylic acid‐4′‐carboxylate) (4,4′‐dinonyl‐2,2′‐bipyridine) (NCS)₂). In combination with an organic hole‐transporting material (spiro‐MeOTAD, 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine) 9, 9′‐spirobifluorene), the C101 sensitizer exhibits an excellent power‐conversion efficiency of 4.5% under AM 1.5 solar (100 mW cm^?2) irradiation in a SSDSC. From electronic‐absorption, transient‐photovoltage‐decay, and impedance measurements it is inferred that extending the π‐conjugation of spectator ligands induces an enhanced light harvesting and retards the charge recombination, thus favoring the photovoltaic performance of a SSDSC.     

Orange and Red Organic Light‐Emitting Devices Employing Neutral Ru(II) Emitters: Rational Design and Prospects for Color Tuning

A new series of charge‐neutral Ru(II ) pyridyl and isoquinoline pyrazolate complexes, [Ru(bppz)₂(PPh₂Me)₂] (bbpz: 3‐tert‐butyl‐5‐pyridyl pyrazolate) ( 1 ), [Ru(fppz)₂(PPh₂Me)₂] (fppz: 3‐trifluoromethyl‐5‐pyridyl pyrazolate) ( 2 ), [Ru(ibpz)₂(PPhMe₂)₂] (ibpz: 3‐tert‐butyl‐5‐(1‐isoquinolyl) pyrazolate) ( 3 ), [Ru(ibpz)₂(PPh₂Me)₂] ( 4 ), [Ru(ifpz)₂(PPh₂Me)₂] (ifpz: 3‐trifluoromethyl‐5‐(1‐isoquinolyl) pyrazolate) ( 5 ), [Ru(ibpz)₂(dpp?)] (dpp? represents cis‐1,2‐bis‐(diphenylphosphino)ethene) ( 6 ), and [Ru(ifpz)₂(dpp?)] ( 7 ), have been synthesized, and their structural, electrochemical, and photophysical properties have been characterized. A comprehensive time‐dependant density functional theory (TDDFT) approach has been used to assign the observed electronic transitions to specific frontier orbital configurations. A multilayer organic light‐emitting device (OLED) using 24 wt % of 5 as the dopant emitter in a 4,4′‐N,N′‐dicarbazolyl‐1,1′‐biphenyl (CBP) host with 4,4′‐bis[N‐(1‐naphthyl)‐N‐phenylamino]biphenyl (NPB) as the hole‐transport layer exhibits saturated red emission with an external quantum efficiency (EQE) of 5.10 %, luminous efficiency of 5.74 cd A^–1, and power efficiency of 2.62 lm W^–1. The incorporation of a thin layer of poly(styrene sulfonate)‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT) between indium tin oxide (ITO) and NPB gave anoptimized device with an EQE of 7.03 %, luminous efficiency of 8.02 cd A^–1, and power efficiency of 2.74 lm W^–1 at 20 mA cm^–2. These values represent a breakthrough in the field of OLEDs using less expensive Ru(II ) metal complexes. The nonionic nature of the complexes as well as their high emission quantum efficiencies and short radiative lifetimes are believed to be the key factors enabling this unprecedented achievement. The prospects for color tuning based on Ru(II ) complexes are also discussed in light of some theoretical calculations.     

High Molar Extinction Coefficient Ion‐Coordinating Ruthenium Sensitizer for Efficient and Stable Mesoscopic Dye‐Sensitized Solar Cells

Ru(4,4‐dicarboxylic acid‐2,2′‐bipyridine) (4,4′‐bis(2‐(4‐(1,4,7,10‐tetraoxyundecyl)phenyl)ethenyl)‐2,2′‐bipyridine) (NCS)₂, a new high molar extinction coefficient ion‐coordinating ruthenium sensitizer was synthesized and characterized using ¹H NMR, Fourier transform IR (FTIR), and UV/vis spectroscopies and cyclic voltammetry. Using this sensitizer in combination with a nonvolatile organic‐solvent‐based electrolyte, we obtain a photovoltaic efficiency of 8.4 % under standard global AM 1.5 sunlight. These devices exhibit excellent stability when subjected to continuous thermal stress at 80 °C or light soaking at 60 °C for 1000 h. An electrochemical impedance spectroscopy study revealed that device stability is maintained by stabilizing the TiO₂/dye/electrolyte and Pt/electrolyte interface during the aging process. The influence of Li⁺ present in the electrolyte on the device photovoltaic parameters was studied, and the FTIR spectral and photovoltage transient study showed that Li⁺ coordinates to the triethyleneoxide methylether side chains on the K60 sensitizer molecules.     

Deciphering the Electroluminescence Behavior of Silver(I)‐Complexes in Light‐Emitting Electrochemical Cells: Limitations and Solutions toward Highly Stable Devices

Ionic transition‐metal complexes based on silver(I) metal core (Ag‐iTMCs) represent an appealing alternative to other iTMCs in solid‐state lighting owing to (i) their low cost and well‐known synthesis, (ii) the tunable bandgap, and (iii) the highly efficient photoluminescence. However, their electroluminescence behavior is barely studied. Herein, the archetypal green‐emitting Ag‐iTMCs, namely [Ag(4,4′‐dimethoxy‐2,2′‐bipyridine)(Xantphos)]X (X = BF₄, PF₆, and ClO₄), are thoughtfully investigated, revealing their electroluminescent features in light‐emitting electrochemical cells (LECs). Despite optimizing device fabrication and operation, luminance of 40 cd m^?2, efficacy of 0.2 cd A^?1, and a very poor stability of 30 s are achieved. This outcome encourages the comprehensive study of the degradation mechanism combining electrochemical impedance spectroscopy, X‐ray diffraction, and cyclic voltammetry techniques. These results point out the irreversible formation of silver nanoclusters under operation strongly limiting the device performance. As such, LECs are further optimized by (i) changing the counterions (PF₆^? and ClO₄^?) and (ii) decoupling electron injection and exciton formation using a double‐layered architecture. The synergy of both approaches leads to a broad exciplex‐like whitish electroluminescence emission (x/y CIE of 0.40/0.44 and color rendering index of 85) with an outstanding improved stability of ≈4 orders of magnitude (>80 h) without losing brightness (35 cd m^?2).     

Archetype Cationic Iridium Complexes and Their Use in Solid‐State Light‐Emitting Electrochemical Cells

The archetype ionic transition‐metal complexes (iTMCs) [Ir(ppy)₂(bpy)][PF₆] and [Ir(ppy)₂(phen)][PF₆], where Hppy = 2‐phenylpyridine, bpy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline, are used as the primary active components in light‐emitting electrochemical cells (LECs). Solution and solid‐state photophysical properties are reported for both complexes and are interpreted with the help of density functional theory calculations. LEC devices based on these archetype complexes exhibit long turn‐on times (70 and 160 h, respectively) and low external quantum efficiencies (～2%) when the complex is used as a pure film. The long turn‐on times are attributed to the low mobility of the counterions. The performance of the devices dramatically improves when small amounts of ionic liquids (ILs) are added to the Ir‐iTMC: the turn‐on time improves drastically (from hours to minutes) and the device current and power efficiency increase by almost one order of magnitude. However, the improvement of the turn‐on time is unfortunately accompanied by a decrease in the stability of the device from 700 h to a few hours. After a careful study of the Ir‐iTMC:IL molar ratios, an optimum between turn‐on time and stability is found at a ratio of 4:1. The performance of the optimized devices using these rather simple complexes is among the best reported to date. This holds great promise for devices that use specially‐designed iTMCs and demonstrates the prospect for LECs as low‐cost light sources.     

Versatile Supramolecular Nanovalves Reconfigured for Light Activation

All autonomous machines share the same requirement—namely, they need some form of energy to perform their operations and nanovalves are no exception. Supramolecular nanovalves constructed from [2]pseudorotaxanes—behaving as dissociatable complexes attached to mesoporous silica which acts as a supporting platform and reservoir—rely on donor‐acceptor and hydrogen bonding interactions between the ring component and the linear component to control the ON and OFF states. The method of operation of these supramolecular nanovalves involves primarily the weakening of these interactions. The [2]pseudorotaxane [BHEEEN ? CBPQT]⁴⁺ [BHEEEN ≡ 1,5‐bis[2‐(2‐(2‐hydroxyethoxy)ethoxy)ethoxy]naphthalene and CBPQT⁴⁺ ≡ cyclobis(paraquat‐p‐phenylene)], when this 1:1 complex is tethered on the surface of the mesoporous silica, constitutes the supramolecular nanovalves. The mesoporous silica is charged against a concentration gradient with luminescence probe molecules, e.g., tris(2,2′‐phenylpyridyl)iridium(III ), Ir(ppy)₃ (ppy = 2,2′‐phenylpyridyl), followed by addition of CBPQT·4Cl to form the tethered [2]pseudorotaxanes. This situation corresponds to the OFF state of the supramolecular nanovalves. Their ON state can be initiated by reducing the CBPQT⁴⁺ ring with NaCNBH₃, thus weakening the complexation and causing dissociation of the CBPQT⁴⁺ ring away from the BHEEEN stalks on the mesoporous silica particles MCM‐41 to bring about ultimately the controlled release of the luminescence probe molecules from the mesoporous silica particles with an average diameter of 600 nm. This kind of functioning supramolecular system can be reconfigured further with built‐in photosensitizers, such as tethered 9‐anthracenecarboxylic acid and tethered [Ru(bpy)₂(bpy(CH₂OH)₂)]²⁺ (bpy = 2,2′‐bipyridine). Upon irradiation with laser light of an appropriate wavelength, the excited photosensitizers transfer electrons to the near‐by CBPQT⁴⁺ rings, reducing them so that they dissociate away from the BHEEEN stalks on the surface of the mesoporous silica particles, leading subsequently to a controlled release of the luminescent probe molecules. This control can be expressed in both a regional and temporal manner by the use of light as the ON/OFF stimulus for the supramolecular nanovalves.     

Efficient Organic Light‐Emitting Diodes based on Sublimable Charged Iridium Phosphorescent Emitters

The synthesis and characterization of two new phosphorescent cationic iridium(III) cyclometalated diimine complexes with formula [Ir( L )₂(N‐N)]⁺(PF₆^–) ( HL = (9,9‐diethyl‐7‐pyridinylfluoren‐2‐yl)diphenylamine); N‐N = 4,4′‐dimethyl‐2,2′‐bipyridine ( 1 ), 4,7‐dimethyl‐1,10‐phenanthroline ( 2 )) are reported. Both complexes are coordinated by cyclometalated ligands consisting of hole‐transporting diphenylamino (DPA)‐ and fluorene‐based 2‐phenylpyridine moieties. Structural information on these heteroleptic complexes has been obtained by using an X‐ray diffraction study of complex 2 . Complexes 1 and 2 are morphologically and thermally stable ionic solids and are good yellow phosphors at room temperature with relatively short lifetimes in both solution and solid phases. These robust iridium complexes can be thermally vacuum‐sublimed and used as phosphorescent dyes for the fabrication of high‐efficiency organic light‐emitting diodes (OLEDs). These devices doped with 5 wt % 1 can produce efficient electrophosphorescence with a maximum brightness of up to 15 610 cd m^–2 and a peak external quantum efficiency of ca. 7 % photons per electron that corresponds to a luminance efficiency of ca. 20 cd A^–1 and a power efficiency of ca. 19 lm W^–1. These results show that charged iridium(III) materials are useful alternative electrophosphors for use in evaporated devices in order to realize highly efficient doped OLEDs.     

Generation of Self‐Assembled 3D Mesostructured SnO2 Thin Films with Highly Crystalline Frameworks

Crack‐free, mesoporous SnO₂ films with highly crystalline pore walls are obtained by evaporation‐induced self‐assembly using a novel amphiphilic block‐copolymer template (“KLE” type, poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide)), which leads to well‐defined arrays of contracted spherical mesopores by suitable heat‐treatment procedures. Because of the improved templating properties of these polymers, a facile heat‐treatment procedure can be applied whilst keeping the mesoscopic order intact up to 600–650 °C. The formation mechanism and the mesostructural evolution are investigated by various state‐of‐the‐art techniques, particularly by a specially constructed 2D small‐angle X‐ray scattering setup. It is found that the main benefit from the polymers is the formation of an ordered mesostructure under the drastic conditions of using molecular Sn precursors (SnCl₄), taking advantage of the large segregation strength of these amphiphiles. Furthermore, it is found that the crystallization mechanism is different from other mesostructured metal oxides such as TiO₂. In the case of SnO₂, a significant degree of crystallization (induced by heat treatment) already starts at quite low temperatures, 250–300 °C. Therefore, this study provides a better understanding of the general parameters governing the preparation of mesoporous metal oxides films with crystalline pore walls.     

Single‐Source Precursors For Synthesizing Bifunctional Periodic Mesoporous Organosilicas

A new class of bifunctional periodic mesoporous organosilicas (PMOs) composed of organosilicate building blocks with two different silicon sites have been synthesized from the single‐source bifunctional organosilica precursors tris(triethoxysilylethyl)ethoxysilane and bis(triethoxysilylethyl)diethoxysilane, respectively denoted MT³‐PMO and DT²‐PMO. The synthesis of these PMOs is achieved by the co‐assembly of a triblock‐copolymer Pluronic P123 template with the bifunctional organosilica precursor under acid‐catalyzed and inorganic‐salt‐assisted conditions. After template removal through solvent extraction, the MT³‐PMO and DT²‐PMO so obtained show well‐ordered mesopores and display large pore diameters (6–7 nm) and pore volumes (0.6–0.8 cm³ g^–1) with a narrow pore‐size distribution and high surface areas (700–800 m³ g^–1).     

Enhanced photovoltaic performance of cross‐linked ruthenium dye with functional cross‐linkers for dye‐sensitized solar cell

Photovoltaic performance of cross‐linkable Ru(2,2′‐bipyridine‐4,4′‐bicarboxylic acid)(4,4′‐bis((4‐vinyl benzyloxy)methyl)‐2,2′‐bipyridine)(NCS)₂ (denoted as RuS dye) adsorbing on TiO₂ mesoporous film was enhanced by polymerizing with either ionic liquid monomer, 1‐(2‐acryloyloxy‐ethyl)‐3‐methyl‐imidazol‐1‐ium iodide (AMImI), to form RuS‐cross‐AMImI or di‐functional acrylic monomer with ether linkage, triethyleneglycodimethacrylate (TGDMA), to form RuS‐cross‐TGDMA. Their cross‐linking properties were investigated by UV–vis spectroscopy by rinsing with 0.1 N NaOH aqueous solution. The power conversion efficiencies (PCEs) of dye‐sensitized solar cells (DSSCs) with RuS‐cross‐AMImI and RuS‐cross‐TGDMA both reached over 8% under standard global air mass 1.5 full sunlight. The increased PCE for DSSCs with RuS‐cross‐AMImI comparing with cross‐linked RuS was attributed to the I⁻ counterion of AMImI increasing the charge regeneration rate of RuS dye, whereas that with RuS‐cross‐TGDMA was attributed to the Li⁺ coordination property of TGDMA. The photovoltaic performance of RuS‐cross‐TGDMA was also slightly better than that of RuS‐cross‐AMImI because of higher open‐circuit photovoltage (V_oc) and short‐circuit photocurrent (J_sc). Its higher V_oc was supported by the Bode plot of impedance under illumination and Nyquist plots at dark, whereas higher J_sc was supported by the incident monochromatic photon‐to‐current conversion efficiency spectra and charge extraction experiments. Copyright © 2013 John Wiley & Sons, Ltd.