Novel Star-Shaped Viologens Containing Phenyl and Triphenylamine Moieties for Electrochromic Applications.

The two star-shaped viologens containing 1,3,5-substituted phenyl (1) and triphenylamine (2) central cores and n-hexyl chains were synthesized and characterized. Both compounds exhibited promising optoelectronic properties and underwent multiple oxidation/reduction processes resulting in various colors. Four possible redox states of tripyridium salt containing a phenyl or triphenylamine core can occur depending on the applied potentials. The wide color range, from colorless through blue, azure to green-gray, was observed during the electrochemical reduction of compound 1. In the case of compound 2, the color change observed during spectroelectrochemical measurements was from yellow to colorless during the cathodic process and from yellow to green during the anodic process. The observed color change for both viologens was reversible. The triphenylamine-cored viologen (2) also exhibited emission in visible range and solvatochromism. It also exhibited luminescence in the solid state when excited with a UV lamp. These studies provide insights into the design of advanced materials for applications in displays.

Photolithographic patterning of viologens containing styrene groups.

A simple method for the patterning of styrene derivatives for electrochromic applications is presented. Novel viologen derivatives containing styrene groups were used in the formation of patternable electrochromic films. The patterning was done via photopolymerization and it shows the possibility of the use of styrene derivatives for the preparation of electrochromic patterns.

Electrochemistry and Electrochromic Performance of a Metallopolymer Formed by Electropolymerization of a Fe(II) Complex with a Triphenylamine-Hydrazone Ligand.

The complex of Fe(II) ions of general formula [FeL2 ](BF4 )2 with triphenylamine-hydrazone ligand L has been synthesized and characterized. Oxidative electropolymerization of the complex proceeded smoothly on the working electrode producing a homogenous thin film of metallopolymer. The film thickness and morphology of the layer was investigated by microscopy techniques such as scanning electron microscopy and atomic force microscopy, and the composition of the film was confirmed by X-ray photoelectron spectroscopy analysis. It was found that fifty successive oxidation/reduction cycles resulted in a 120 nm thick film on the electrode surface. The metallopolymer was also characterized using cyclic voltammetry and spectroelectrochemical methods. The film was found to change its color from yellow to green-blue, exhibit high change in transmittance of 60 % at 770 nm, and possess good electrochemical stability during 375 cycles of switching of the potential between -0.1 V and +1.5 V, owing to the presence of metal ions that link two ligand molecules resulting in formation of highly cross-linked film. The switching times (coloration and bleaching) were calculated to be 34.2 s and 7.3 s, respectively. Coloration efficiency of the formed film of polymeric complex was found to be 144 cm2 C-1 .

Reductive Electropolymerization and Electrochromism of Iron(II) Complex with Styrene-Based Ligand.

The benzimidazole-based ligand containing polymerizable styrene group has been prepared via condensation of picolinaldehyde derivative containing styrene moiety and benzimidazole-based hydrazine. The ligand reacted with iron(II) tetrafluoroborate and iron(II) trifluoromethanesulfonate giving red-brown complexes of Fe(II) ions of formula [FeL2]X2, where X = CF3SO3- (1) or BF4- (2). Reductive electropolymerization was used to obtain a thin layer of the polymeric complex, poly-1. Further investigation of electrochemical properties of the compound by cyclic voltammetry showed two quasi-reversible redox processes assigned to electrooxidation and electroreduction of the polymer. Spectroelectrochemical measurements confirmed that the polymer undergoes the color changes during oxidation and reduction process. The polymer in its neutral state (Fe(II)) is yellow and it exhibits absorption band at 370 nm, after oxidation to Fe(III) state absorption band shifts to 350 nm and the polymer is almost colorless. While the metal ions are reduced to Fe(I) absorption band at around 410 nm has been observed and the polymer changed its color to intense yellow. The stability of the polymer during multiple oxidation/reduction cycles has also been investigated.

Toward Electrochromic Metallopolymers: Synthesis and Properties of Polyazomethines Based on Complexes of Transition-Metal Ions.

The tridentate ligand L and its complexes with transition-metal ions have been prepared and characterized. The polycondensation reactions of transition-metal complexes with different dialdehydes led to the formation of transition-metal-complex-based polyazomethines, which have been obtained by on-substrate polymerization, and their electrochemical and electrochromic performance have been investigated. The most interesting properties are exhibited by polymers of Fe(II) and Cu(II) ions obtained by the reaction of the appropriate complexes with a triphenylamine-based dialdehyde. Fe(II) polymer P1 undergoes a reversible oxidation/reduction process and a color change from orange to gray due to the oxidation of Fe(II) to Fe(III) ions concomitant with the oxidation of the triphenylamine group. Its electrochromic properties such as long-term stability, switching times, and coloration efficiencies have been investigated, providing evidence of the utility of the on-substrate polycondensation reaction in the formation of thin films of electrochromic metallopolymers.

Electrochemical and Solvent-Mediated Visible-to-Near-Infrared Spectroscopic Switching of Benzoselenadiazole Fluorophores.

A series of electronic push-pull, pull-pull, and push fluorophores has been prepared from a benzoselenadiazole core so that their spectroscopic, electrochemical, spectro-electrochemical, and spectro-electrofluorescence properties could be examined. The emission wavelengths and fluorescence quantum yields (Φfl ) of the N,N-dimethyl fluorophores were contingent on the solvent polarity and they ranged from 615 to 850 nm in aprotic solvents. The positive solvatochromism and the quenched Φfl in polar solvents were consistent with an intramolecular charge-transfer state (ICT). Meanwhile, a locally excited state (LE) was assigned in nonpolar solvents from the blue-shifted emission and high Φfl . The N,N-dimethylamine fluorophores examined could be both electrochemically oxidized and reduced, whereas the symmetric dinitro pull-pull derivative could be only reversibly reduced. Courtesy of their electrochemical reversibility, the fluorophores could reversibly change color from yellow to blue with an applied potential in addition to switching off their emission. The absorption of the electrochemically generated intermediates of the N,N-dimethyl derivatives spanned 500 nm over the visible and the NIR regions. The colors could be switched for upwards of two hours with applied potential, illustrating their potential use as electroactive materials in electrochromic devices.

Yellow-to-brown and yellow-to-green electrochromic devices based on complexes of transition metal ions with a triphenylamine-based ligand.

Transmissive-to-colored electrochromism has been achieved by combination of MLCT of transition metal complexes with the electrochromic properties of ligand molecules. The color transitions were from yellow to dark brown for the Fe(ii) complex, yellow to orange to bluish-green for the Co(ii) complex and yellow to green for the Zn(ii) complex. By using a metal ion-ligand coordination approach, the self-assembly of hydrazone-based ligands containing a triphenylamine group with appropriate metal salts (FeCl2, Co(ClO4)2 and Zn(BF4)2) produced novel complexes of the general formula [ML2]X2. The isolated complexes were characterized by spectroscopic methods, and the Co(ii) complex also by X-ray diffraction analysis. Thin films of the complexes have been obtained by a spray-coating method and they were used in the construction of electrochromic devices, which showed good electrochromic stability, a high color contrast of 47.5% for Fe(ii), 37.2% for Co(ii) and 33.7% for Zn(ii) complexes and fast coloring and bleaching times.

New Artificial Biomimetic Enzyme Analogues based on Iron(II/III) Schiff Base Complexes: An Effect of (Benz)imidazole Organic Moieties on Phenoxazinone Synthase and DNA Recognition.

Elucidation of the structure and function of biomolecules provides us knowledge that can be transferred into the generation of new materials and eventually applications in e.g., catalysis or bioassays. The main problems, however, concern the complexity of the natural systems and their limited availability, which necessitates utilization of simple biomimetic analogues that are, to a certain degree, similar in terms of structure and thus behaviour. We have, therefore, devised a small library of six tridentate N-heterocyclic coordinating agents (L1-L6), which, upon complexation, form two groups of artificial, monometallic non-heme iron species. Utilization of iron(III) chloride leads to the formation of the 1:1 (Fe:Ln) 'open' complexes, whereas iron(II) trifluoromethanosulfonate allows for the synthesis of 1:2 (M:Ln) 'closed' systems. The structural differences between the individual complexes are a result of the information encoded within the metallic centre and the chosen counterion, whereas the organic scaffold influences the observed properties. Indeed, the number and nature of the external hydrogen bond donors coming from the presence of (benz)imidazole moieties in the ligand framework are responsible for the observed biological behaviour in terms of mimicking phenoxazinone synthase activity and interaction with DNA.

Synthesis and Characterization of Liquid-Crystalline Tetraoxapentacene Derivatives Exhibiting Aggregation-Induced Emission.

A series of new tetrakis(dialkoxyphenyl) dicyanotetraoxapentacene derivatives (1 a-c) were prepared by reaction of the appropriate terphenyl diols with tetrafluoroterephthalonitrile in good yields. Compounds 1 b and 1 c, which bear hexyloxy and decyloxy side chains, exhibited columnar hexagonal mesophases, as shown by polarized optical microscopy, variable-temperature powder X-ray diffraction, and differential scanning calorimetry. Single-crystal X-ray diffraction of methoxy-substituted 1 a revealed that the dicyanotetraoxapentacene core is highly planar, consistent with the notion that these molecules are able to stack in columnar mesophases. A detailed photophysical characterization showed that these compounds exhibit aggregation-induced emission in solution, emission in nonpolar solvents, weak emission in polar solvents, and strong emission in the solid state both as powder and in thin films. These observations are consistent with a weakly emissive charge-transfer state in polar solvents and a more highly emissive locally excited state in nonpolar solvents.

Coordination properties of N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine with d- and f-electron ions: crystal structure, stability in solution, spectroscopic and spectroelectrochemical studies.

Template reaction between 5-methylsalicylaldehyde and 2-hydroxy-1,3-propanediamine in the presence of copper ion led to dinuclear and mononuclear copper(ii) complexes [Cu2L(CH3COO)(CH3OH)](CH3OH) (1) and [CuHL](CH3OH) (2), where H3L is N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine. The result of the reactions between 5-methylsalicylaldehyde and 2-hydroxy-1,3-propanediamine in the presence of lanthanide ions and/or copper(ii) ion was N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine (H3L B) or [CuHL](CH3OH) (2), respectively. Structures of the compounds were determined by single-crystal X-ray diffraction and physicochemical methods. The microstructures and phase compositions of crystals were studied by scanning electron microscopy (SEM). In dinuclear complex [Cu2L(CH3COO)(CH3OH)](CH3OH) (1), two copper(ii) ions are bond to one H3L ligand and one acetate ion. Coordination modes of the two copper centers are different: the geometry of copper 1 is almost ideal square-planar, while that for copper 2 can be described as tetragonal pyramidal. In complex [CuHL](CH3OH) (2), the copper(ii) ion is four coordinated and the coordination, rather than square-planar, can be described as flattened tetrahedral. Formation of complexes between copper(ii) or lanthanide ions with N,N'-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine (H3L) was also studied in solution by pH potentiometry. It should be mentioned that the complexes of lanthanide ions exist only in solution. Additionally, the salen-type ligand H3L and its dinuclear and mononuclear copper(ii) complexes were studied by cyclic voltammetry, and their spectroelectrochemical properties were examined.

Visible-to-NIR Electrochromic Device Prepared from a Thermally Polymerizable Electroactive Organic Monomer.

A monomer (1) consisting of a benzothiadiazole core flanked by two triphenylamines and two styrene pendant moieties was prepared. The monomer was fluorescent with its emission spanning 145 nm in the visible, contingent on the organic solvent used for the measurement. In addition to its positive solvatochromism, the absolute fluorescence quantum yield (Φfl) was consistently >20% with values >80% being measured in hexane, toluene, diethyl ether, and toluene. 1 could be reversibly oxidized with an oxidation potential of 880 mV vs SCE. The monomer could be immobilized on ITO-coated glass substrates. The resulting 425 nm thick immobilized film (poly-1) was 15% thinner than the monomer coating deposited by spray- and spin-coating. The electroactive film did not delaminate from the electrode upon either washing or cycling electrochemically between its oxidized and neutral states. Its absorption at 460 nm bleached upon electrochemical oxidation with the formation of a strong absorption at 880 nm and in the NIR, similar to 1. The perceived reversible color change with applied potential switched between yellow and gray. The fluorescence intensity of poly-1 could be switched with applied potentials. A passive transmissive device prepared from poly-1 was both electrochromic and fluorochromic, exhibiting reversible color change and fluorescence quenching.

Hydrogen-Bond and Supramolecular-Contact Mediated Fluorescence Enhancement of Electrochromic Azomethines.

An electronic push-pull fluorophore consisting of an intrinsically fluorescent central fluorene capped with two diaminophenyl groups was prepared. An aminothiophene was conjugated to the two flanking diphenylamines through a fluorescent quenching azomethine bond. X-ray crystallographic analysis confirmed that the fluorophore formed multiple intermolecular supramolecular bonds. It formed two hydrogen bonds involving a terminal amine, resulting in an antiparallel supramolecular dimer. Hydrogen bonding was also confirmed by FTIR and NMR spectroscopic analyses, and further validated theoretically by DFT calculations. Intrinsic fluorescence quenching modes could be reduced by intermolecular supramolecular contacts. These contacts could be engaged at high concentrations and in thin films, resulting in fluorescence enhancement. The fluorescence of the fluorophore could also be restored to an intensity similar to its azomethine-free counterpart with the addition of water in >50 % v/v in tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and acetonitrile. The fluorophore also exhibited reversible oxidation and its color could be switched between yellow and blue when oxidized. Reversible electrochemically mediated fluorescence turn-off on turn-on was also possible.

Novel self-assembled supramolecular architectures of Mn(II) ions with a hybrid pyrazine-bipyridine ligand.

A new hybrid pyrazine-bipyridine ligand L (C26H20N6) and its complexes with Mn(NO3)2, Mn(ClO4)2, MnCl2 and MnBr2 have been synthesised. By the self-assembly of L and Mn(II) ions three different kinds of supramolecular complexes have been obtained: binuclear baguette complex [Mn2L(H2O)6](NO3)4·2.5H2O 1 and tetranuclear [2 × 2] grid-type complex [Mn4L4](ClO4)8·2.5(CH3CN)·2CH3OH 2 and mononuclear complexes [MnL2]X2 (where X = Cl(-)3 and X = Br(-)4). Crystal structures and magnetic properties of Mn(II) complexes 1 and 2 have been also investigated. The crystal structures reveal that in both 1 and 2 complexes the Mn(II) ions have coordination number 6 and distorted octahedral coordination geometry. In 2 four metal cations and four ligands have assembled into a grid-type [2 × 2] array, with a perchlorate anion occupying the central cavity, with clearly a good fit for the center of the cavity. The perchlorate anion, in contrast to the nitrate anion, probably acts as a template in the formation of tetranuclear grid-type complexes. Magnetic susceptibility measurements indicate that the Mn(II) ions are all high spin, and in both 1 and 2 complexes there are weak antiferromagnetic interactions between Mn(II) ions.

Self-assembly of transition metal ion complexes of a hybrid pyrazine-terpyridine ligand.

A new hybrid pyrazine-terpyridine ligand L (C(34)H(22)N(8)) and its complexes with different transition metal ions, M (M = Mn(II) 1, Zn(II) 2, Fe(II) 3, Co(II) 4, Cu(II) 5 and Cd(II) 6), have been synthesised. In the presence of a nitrate counter-anion, both Cu(II) and Cd(II) give complexes in which the ratio M:L is 2:1, whereas with perchlorate, trifluoromethanesulfonate or tetrafluoroborate, the other metal ions provide solids in which this ratio is 1:1. From mass spectral measurements and a single crystal, X-ray structure determination for the Fe(II) complex 3, however, all the latter species are concluded to be 2:2 complexes. Both the Fe(II) complex 3 and the Co(II) complex 4, generated from tetrafluoroborate reactant salts, have the composition [M(2)L(2)F(2)(H(2)O)](BF(4))(2), the presence of fluoride ligands being presumed to reflect the abstraction of fluoride ions from tetrafluoroborate by the metal ions under the preparative conditions. The crystal structure of complex 3 shows the Fe(II) centres to be inequivalent, one being high-spin and heptacoordinate with a FeN(4)F(2)O coordination sphere, the other low-spin and octahedral with a FeN(6) sphere. The two ligand molecules differ markedly, one being heptadentate, the other clearly "hypodentate", with only three N-donor atoms of a terpyridine-like arm coordinated, although their conformations are similar, showing significant differences from that of C(2) symmetry found for the free ligand by a crystal structure determination. Mass spectra are consistent with the Cu(II) and Cd(II) complexes having the composition [M(2)L(H(2)O)(n)(NO(3))(4-n)](NO(3))(4-n), and the weak antiferromagnetic coupling observed for the Cu(II) complex is consistent with a preliminary crystal structure determination which indicates that the two Cu(II) centres are not bridged by a pyrazine unit.

Self-assembly of quaterpyridine ligands and Cu+ cation into helical complexes of 2:2 stoichiometry under electrospray ionisation conditions.

Solutions containing quaterpyridine ligand 1 and Cu(2+) cation were analysed by electrospray ionisation mass spectrometry (ESI-MS). It was found that copper reduction under ESI conditions and self-assembly of 1 and Cu(I) led to the formation of the 2:2 stoichiometry complex. Such stoichiometry is characteristic of helical complex of quaterpyridine ligand with Cu(I). The isotope pattern characteristic of [Cu(2)1(2)](2+) ion and different from that of [Cu1](+) ion, is observed. When using methanol as solvent, only [Cu(2)1(2)](2+) ions are observed in mass spectrum obtained at low cone voltage. At higher cone voltage [Cu(2)1(2)](2+) ion easy dissociates producing [Cu1](+) ion. When using other solvents studied, water and acetonitrile, 2:2 stoichiometry complex is formed, but along with complexes of other stoichiometries. Helical complex was not observed for silver cation for which only 1:1 stoichiometry complex was observed (ion [Ag1](+)).