Exploiting Mixed Valence Charge Transfer for Electrochromic and Electrofluorochromic Use.

An asymmetric mixed valence fluorophore with two different electron rich termini was investigated as a dual-role active material for electrochromism and electrofluorochromism. The fluorescence quantum yield (Φfl) and emission wavelength of the fluorophore were dependent on solvent polarity. The quantum yield of the material in an electrolyte gel, on a glass substrate and in a device was 40 %, 20 % and 13 % respectively. The fluorophore further underwent two near-simultaneous electrochemical oxidations. The first oxidation resulted in a 1000 nm red shift in the absorption to broadly absorb in the NIR, corresponding to the intervalence charge transfer (IVCT). Whereas the second oxidation led to a perceived green color at 715 nm with the extinction of the NIR absorbing IVCT. Owing to the dissymmetry of the fluorophore along with its two unique oxidation sites, the IVCT gives rise to a mixed valence transfer charge (MVCT). The coloration efficiency of the fluorophore in both solution and a device was 1433 and 200 cm2 C-1, respectively. The fluorescence intensity could be reversibly modulated electrochemically. The photoemission intensity of the fluorophore was modulated with applied potential in an operating electrochromic/electrofluorochromic device. Both the dual electrochromic and the electrofluorochromic behavior of the fluorophore were demonstrated.

Survey of Recent Advances in Molecular Fluorophores, Unconjugated Polymers, and Emerging Functional Materials Designed for Electrofluorochromic Use.

In this review, recent advances that exploit the intrinsic emission of organic materials for reversibly modulating their intensity with applied potential are surveyed. Key design strategies that have been adopted during the past five years for developing such electrofluorochromic materials are presented, focusing on molecular fluorophores that are coupled with redox-active moieties, intrinsically electroactive molecular fluorophores, and unconjugated emissive organic polymers. The structural effects, main challenges, and strides toward addressing the limitations of emerging fluorescent materials that are electrochemically responsive are surveyed, along with how these can be adapted for their use in electrofluorochromic devices.

An intrinsically stretchable and bendable electrochromic device.

Stretchable electrochromic devices (ECDs) were fabricated from electrospun PEDOT:PSS (poly(3, 4-ethylenedioxythiophene):polystyrene sulfonate) fibers. Stretchable and transparent electrodes with a sheet resistance of 1200 Ω sq-1were prepared by depositing the conductive fibers on elastomeric substrates that were prepared from polydimethylsiloxane. The conductive substrates replaced the ITO coated glass electrodes that are typically used in ECDs. The functioning device was prepared from a flexible chitosan electrolytic gel and a 4, 7-bis(4-diphenylaminophenyl)-2, 1, 3-benzothiaziazole (TPA-BZT-TPA) electrochrome that were deposited on the streatchable transparent electrodes. The assembled device could be stretched to 150% its original length and bent to a curvature of 0.1. The device could be operated and switched between its yellow (off) and blue (on) states while being stretched and bent with a maximum contrast ΔT ≈ 30% at 805 nm and a coloration efficiency of 168 cm2C-1. The stretchable device had an electrochromic contrast that was 30% greater than its counterpart that was prepared from conventional ITO-glass electrodes. The critical composition required for making devices truly stretchable was possible by evaluating the performance of five types of devices consisting of different layers.

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.

Synthesis of Emissive Heteroacene Derivatives via Nucleophilic Aromatic Substitution.

A synthetic approach for preparing a variety of heterocyclic tetrahydropentacene derivatives via nucleophilic aromatic substitution reactions of bidentate nucleophiles and tetrafluoroterephthalonitrile was developed. X-ray crystallography of several products revealed that the compounds containing oxygen and nitrogen heteroatoms are highly planar and engage in π-stacking, while the compounds containing sulfur are bent and do not stack as effectively. The compounds were also highly emissive, and the heteroatom had a significant impact on the emission and electrochemical properties.

Understanding Color Tuning and Reversible Oxidation of Conjugated Azomethines.

With the aim of achieving reversible oxidation and color tuning, the effect of the central aromatic on the spectroscopic, electrochemical, and spectrochemical properties of a series of electrochromic azomethine triads was investigated. The absorption of the alkylated thiophene derivatives was blue-shifted relative to their unalkylated counterparts when the central aromatic was either a bi- or terthiophene. It was further found that the alkylated thiophene derivatives had larger Stokes shifts than their unsubstituted counterparts. Theoretical calculations demonstrated that the torsion angles of these alkylated cores with respect to the flanking azomethines were responsible for the spectroscopic effects. While the electrochemical oxidation potential of the triads varied by only 100 mV, the reversibility of their anodic process was contingent on the central aromatic. The absorption of the electrochemically produced state red-shifted between 165 and 280 nm from its corresponding neutral state, leading to perceived color changes between orange and blue. Reversible color changes were chemically mediated with ferric chloride/hydrazine. The absorption of the chemically oxidized state shifted between 155 and 220 nm from the corresponding neutral state, contingent on the central aromatic. The palette of perceived colors that was possible with oxidation included orange, yellow, blue, and gray.

Surface immobilized azomethine for multiple component exchange.

Diazonium chemistry concomitant with in situ electrochemical reduction was used to graft an aryl aldehyde to indium-tin oxide (ITO) coated glass substrates. This served as an anchor for preparing electroactive azomethines that were covalently bonded to the transparent electrode. The immobilized azomethines could undergo multiple step-wise component exchanges with different arylamines. The write-erase-write sequences were electrochemically confirmed. The azomethines could also be reversibly hydrolyzed. This was exploited for multiple azomethine-hydrolysis cycles resulting in discrete electroactive immobilized azomethines. The erase-rewrite sequences were also electrochemically confirmed.

Unusually high fluorescence quantum yield of a homopolyfluorenylazomethine--towards a universal fluorophore.

The absolute fluorescence quantum yield (Φfl) of a polyfluorenyl azomethine homopolymer was measured as a function of solvent polarity. The solvent induced and temperature dependent fluorescence of the homopolymer were also investigated and they were compared to the corresponding monomer and copolymer. The Φfl of the homopolymer was consistent (45-70%), regardless of solvent polarity with Stokes shifts up to 7460 cm(-1) in ethanol. In contrast, the Φfl of its corresponding monomer decreased from 60% in ethanol to 1% in toluene, whereas a Φfl < 5% for its analogous copolymer was measured. Moderate fluorescence yields (Φfl ≈ 25%) were also possible in thin film when co-depositing the homopolymer with PMMA. Cryofluorescence was used to probe the excited state deactivation modes. Deactivation by internal conversion was found to compete with fluorescence. The fluorescence deactivation pathways of the homopolymer and its corresponding monomer could be suppressed at 77 K, resulting in fluorescence turn-on. Both fluorophores were found to detect nitroaromatics.

On-Substrate Preparation of a Poly(triphenylamino azomethine) for Electrochromic Devices.

An electroactive polyazomethine was prepared directly on a transparent electrode by the polycondensation of bis(triphenylamine) dialdehyde and its complementary methoxytriphenylamine diamine. The spray-and-bake method of coating the electrode for preparing electrochromic layers could be upscaled to prepare working devices larger than standard test devices. The film prepared by thermally annealing the complementary monomers was both electroactive and switched its color with an applied potential. The yellow electrochromic polyazomethine could be electrochemically oxidized reversibly to obtain a blue film. The electrochromic test device fabricated from the polyazomethine was operated upwards of 1 h for performance assessment. The electrochromic response times of the electrochromic device were ca. 3.3 and 1.2 s for the coloration and bleaching, respectively. The upscaled device prepared by the straightforward coating approach had consistent metrics with the small-area test device.

Tuning the dimensionality in chiral and racemic organic/tin hybrids with halides.

Chiral 1D tin iodides EBASnI3 were synthesized while incorporating enantiomerically pure and racemic ethylbenzylammonium (EBA) cations between the 1D shared inorganic corners. The dimensionality was reduced to 0D when replacing iodine with bromine. In all the cases, the presence of hydrogen bonds was observed between the organic part and the inorganic part, while transfer of chirality was evidenced for the EBASnI3 enantiomerically pure compounds.

Insight into the isoelectronic character of azomethines and vinylenes using representative models: a spectroscopic and electrochemical study.

A series of azomethine and vinylene dyad and triad analogues were prepared. Their absorbance, fluorescence, and redox properties were examined experimentally and theoretically using density functional theory (DFT) calculations. These measurements were done to determine the effect of the heteroatom of the azomethine relative to its all-carbon counterpart and to assess the isoelectronic character of the two bonds. The orientation of the azomethine was found to have little effect on the absorbance, fluorescence, and electrochemical properties. In contrast, the spectral and electrochemical properties were highly contingent on the electronic groups and degree of conjugation. The spectral properties could be tuned 200 nm across the visible region. More importantly, the heteroatom in the conjugated bond was found to give rise to only a 20 nm bathochromic shift in the absorbance and fluorescence spectra. The fluorescence quantum yield (ΦFl) of the vinylene derivatives varied between 5% and 20% with fluorescence quenching occurring by photoisomerization from the E to Z isomers. In contrast, the fluorescence of the analogous azomethine derivatives was completely quenched. The collective spectroscopic and electrochemical ab initio DFT data additionally confirmed that the azomethine and its analogous vinylene are isoelectronic. It was also found that a conjugated thiophene vinylene dyad with primary amines in the α,α'-positions could be prepared and isolated. The compound was stable under aerobic conditions providing electron withdrawing (either ester or nitrile) groups were located in the adjacent positions.

Photophysical and electrochemical investigations of the fluorescent probe, 4,4'-bis(2-benzoxazolyl)stilbene.

In solution, 4,4'-bis(2-benzoxazolyl)stilbene (BBS) was found to exhibit consistently high absolute fluorescence quantum yields (Φ(fl) ≥ 0.88) and a monoexponential lifetime, both independent of BBS concentration. The BBS steady-state and time-resolved photophysics were investigated by different techniques to understand the various deactivation pathways. Nonradiative deactivation of BBS singlet excited state by intersystem crossing was found to be negligible. Other than fluorescence, the excited state of BBS was found to be deactivated by trans-cis photoisomerization. At low concentrations (≈5 µg/mL), UV spectroscopy and laser flash photolysis showed concordant results that the photoinduced cis isomer gradually replaced the original absorption spectrum of the pure trans isomer. However, at high concentrations (≈0.2 mg/mL), (1)H NMR and DOSY measurements confirmed that irradiating BBS at 350 nm induced a conversion from the trans-BBS into its cis isomer by photoisomerization. It was further found that the stilbene moiety of both isomers was photocleaved. The resulting photoproduct was an aldehyde that was oxidized under ambient conditions to its corresponding carboxylic acid, i.e., 4-(1,3-benzoxazol-2-yl)benzoic acid. The structure of the photoproduct was unequivocally confirmed by X-ray diffraction. Spectroscopic investigation of BBS showed a limited photoisomerization after irradiation at 350 nm of a trans solution. The BBS electrochemistry showed irreversible oxidation, resulting in an unstable and highly reactive radical cation. Similarly, the cathodic process was also found to be irreversible, giving rise to a radical anion and showing its n-doping character.

The six-membered-ring azomethine N-((E)-{5-[(E)-(pyridin-3-ylimino)methyl]thiophen-2-yl}methylidene)pyridin-3-amine.

The title compound, C16H12N4S, forms a three-dimensional layered network structure via intermolecular hydrogen bonding and π-stacking. The azomethine molecule adopts the thermodynamically stable E regioisomer and the pyridine substituents are antiperiplanar. The mean planes of the pyridine rings and the azomethine group to which they are connected are twisted by 27.27 (5) and 33.60 (5)°. The electrochemical energy gap of 2.3 eV based on the HOMO-LUMO energy difference is in agreement with the spectroscopically derived value.

α,α'-N-Boc-substituted bi- and terthiophenes: fluorescent precursors for functional materials.

Fluorescent α,α'-diamide substituted bi- and terthiophene derivatives were prepared by Stille and Suzuki couplings. Their one-pot deprotection and coupling with 2-thiophene carboxaldehyde led to stable conjugated azomethines. These exhibited electrochromic properties, and they were used to fabricate a working electrochromic device.

Solvatochromic investigation of highly fluorescent 2-aminobithiophene derivatives.

The solvatochromic and electrochemical properties of electronic push-pull 2-aminobithiophenes consisting of an aldehyde and nitro withdrawing groups were examined. With the use of an integrating sphere, the absolute quantum yields of the bithiophenes were measured. They were found to be highly fluorescent (Φfl > 70%), provided the nitro group was not located in the 4'-position. High fluorescence yields were observed regardless of solvent, except for alcohols, notably methanol and ethanol. Cryofluorescence was used to probe the bithiophene temperature dependent excited state deactivation modes. The singlet excited state deactivation mode other than fluorescence was found to be internal conversion involving rotation around the thiophene-thiophene bond. Deactivation by intersystem crossing to the triplet state occurred in ca. 40% only for the unsubstituted 2-aminobithiophene. In contrast, the fluorescence was quenched by photoinduced intramolecular electron transfer when the nitro group was located in the 4'-position of the bithiophene. Both the absorbance and fluorescence of the bithiophenes were found to be solvatochromic with more pronounced solvent dependent shifts being observed with the fluorescence. In fact, both the fluorescence and Stokes shifts were linearly dependent on the ET(30) solvent parameter. Deviations from the linear trend of the Stokes shift with ET(30) were observed in ethanol and methanol as a result of intermolecular hydrogen abstraction from the solvent and by the excited nitro group. The oxidation potential of the bithiophenes was also highly dependent on the type and number of the electron withdrawing substituents, with values ranging between 0.8 and 1.2 V vs. SCE.

Oligofluorenes as polymeric model compounds for providing insight into the triplets of ketone and ketylimine derivatives.

A series of oligofluorenes ranging between one and three repeating units were prepared as structurally well-defined representative models of polyfluorenes. The photophysics of the oligofluorene models were investigated both by laser flash photolysis and steady-state fluorescence. The effects of the ketone and ketylimine functional groups in the 9-position on the photophysical properties, notably the triplet quantum yield (Φ(TT)) by intersystem crossing and the absolute fluorescence quantum yields (Φ(fl)), were investigated. The singlet depletion method was used to determine both the Φ(TT) and molar absorption coefficients of the observed triplets (ε(TT)). Meanwhile, the absolute Φ(fl) were determined using an integrating sphere. It was found that both the ketone and ketylimine substituents and the degree of oligomerization contributed to quenching the oligofluorene fluorescence. For example, the Φ(fl) was quenched 5-fold with the ketylimine and ketone substituents for the bifluorenyl derivatives compared to their corresponding 9,9-dihexyl bifluorenyl counterparts. Meanwhile, the Φ(fl) quenching increased 14 times with the trifluorenyl ketone and ketylimine derivatives. Measured Φ(TT) values ranged between 22 and 43% for the difluorenyl derivatives with ε(TT) on the order of 13 000 cm(-1) M(-1). The Φ(TT) decreased to <10% concomitant with doubling of the ε(TT) when the degree of oligomerization was increased to 3. A new fluorescence emission at 545 nm formed at low temperatures for the ketone and ketylimine oligofluorene derivatives. The emission intensity was dependent on the temperature, and it disappeared at room temperature.

2-[(E)-(Pyridin-2-yl-methyl-idene)amino]-thio-phene-3-carbonitrile.

In the title compound, C11H7N3S, the thio-phene and pyridine rings are coplanar, forming a dihedral angle of 3.89 (7)°. The conformation about the C=N bond [1.2795 (18) Å] is E. In the crystal, translationally related mol-ecules along the a axis form weak π-π inter-actions [centroid-centroid distance = 3.8451 (8) Å] between the thio-phene rings.

Diethyl 2,5-bis-[(1E)-(1H-pyrrol-2-yl-methyl-idene)amino]-thio-phene-3,4-dicarboxyl-ate.

In the crystal structure of the title compound, C(20)H(20)N(4)O(4)S, the azomethine group adopt E conformations. The pyrrole units are twisted by 10.31 (4) and 18.90 (5)° with respect to the central thio-phene ring. The three-dimensional network is close packed and involves N-H⋯O, N-H⋯N, C-H⋯N and C-H⋯O hydrogen bonding.

Diethyl 2,5-bis-[(2,3-dihydro-thieno[3,4-b][1,4]dioxin-5-yl)methyl-idene-amino]-thio-phene-3,4-dicarboxyl-ate acetone monosolvate.

The unique 3,4-ethyl-ene-dioxy-thio-phene (EDOT) unit of the title compound, C(24)H(22)N(2)O(8)S(3)·C(3)H(6)O, is twisted by 1.9 (3)° relative to the central thio-phene ring. The three heterocyclic units are anti-periplanar. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds connect the heterocycles. π-π interactions occur between the central thiophene and the imine bond of the molecule [distance between the ring centroid of the ring and the azomethine bond = 3.413 (3) Å.

Diethyl 2-amino-5-[(E)-(furan-2-yl-methyl-idene)amino]-thio-phene-3,4-di-carboxyl-ate.

In the crystal structure of the title compound, C(15)H(16)N(2)O(5)S, the azomethine adopts the E configuration. The two heterocyclic rings adopt an anti-periplanar orientation. The mean planes of the thio-phene and furan rings are twisted by 2.51 (4)°. The crystal structure exhibits inter-molecular N-H⋯O hydrogen bonding. π-π stacking is also observed, the centroid-to-centroid distance being 3.770 (4) Å.