Reversible Reduction Processes Research Articles

A triangular prismatic hexanuclear iridium(iii) complex bridged by flavin analogues showing reversible redox processes

[Ir(6)(μ-alloCl(2)(2-))(3)(Cp*)(6)(OH)(3)](PF(6))(3) (1) having 7,8-dichloroalloxazine dianion (alloCl(2)(2-)) as bridging ligands was synthesized and characterized by X-ray crystallography, spectroscopic and electrochemical measurements. The alloxazine ligands showed unprecedented coordination modes to link the six Ir(III) centres. The complex exhibited remarkable stability and reversible six-electron redox processes at the bridging alloxazine ligands in organic solvents. The first reversible reduction process occurred on each of three alloxazine ligands in 1 to produce a three-electron-reduced species, [Ir(III)(6)Cp*(6)(μ-alloCl(2)˙(3-))(3)(OH)(3)], and was observed as an apparent one-step reduction process at -0.65 V (vs. Fc(0/+)). The second reversible reduction process on each of the three alloxazine ligands in 1 was recorded at almost the same potential, -0.78 V (vs. Fc(0/+)), to afford the six-electron-reduced form, [Ir(III)(6)Cp*(6)(μ-alloCl(2)(4-))(3)(OH)(3)](3-). The radical anion of the alloxazine derivative was detected by EPR measurements at room temperature. After the six-electron reduction of 1 with cobaltocene, the backward oxidation processes of reduced forms with p-chloranil were traced by UV-Vis spectroscopy to confirm the recovery of the original spectrum of 1.

2,5-Thiophene substituted spirobisiloles – synthesis, characterization, electrochemical properties and performance in bulk heterojunction solar cells

New spirobisilole molecules containing thienyl (DTSBS) and bis-thienyl (BBTSBS) electron donor groups have been synthesized for use as the donor material in bulk-heterojunction solar cells together with PCBM. The spectroscopic, electrochemical and thermal properties of DTSBS and BBTSBS have been investigated. All these new spirobisiloles exhibit excellent thermal stability. Cyclic voltammetry measurements revealed reversible and irreversible oxidation and irreversible reduction processes. The highest occupied and lowest unoccupied molecular orbital (HOMO/LUMO) energy levels were determined from electrochemical measurements and DFT calculations. The HOMO/LUMO energy levels were estimated to lie in the range of −5.2 to −2.3 eV for DTSBS and −4.9 to −2.6 eV for BBTSBS. For both compounds, electropolymerization processes occur at potentials higher than 1.5 V leading to low band gap electrogenerated polymers. Spin-coating-deposited bulk-heterojunction solar cells fabricated with the novel spirobisiloles as donor and PCBM as acceptor displayed open-circuit voltages up to 0.4 V, short-circuit currents around 0.5 mA cm−2, and power conversion efficiencies approaching 0.1%.

Dithienylbenzothiadiazole-Based Donor-Acceptor Organic Semiconductors and Effect of End Capping Groups on Organic Field Effect Transistor Performance

Donor-Acceptor-Donor (D-A-D) based conjugated molecules 4,7-bis(5-(4-butoxyphenyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (BOP-TBT) and 4,7-bis(5-(4-trifluoromethyl)phenyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (TFP-TBT) using thiophene-benzothiadiazole-thiophene central core with trifluoromethyl phenyl and butoxyphenyl end capping groups were designed and synthesised via Suzuki coupling. Optical, electrochemical, thermal, and organic field effect transistor (OFET) device properties of BOP-TBT and TFP-TBT were investigated. Both small molecules possess two absorption bands. Optical band gaps were calculated from the absorption cut off to be in the range of 2.06–2.25 eV. Cyclic voltammetry indicated reversible oxidation and reduction processes and the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were calculated to be in the range of 5.15–5.40 eV and 3.25–3.62 eV, respectively. Upon testing both materials for OFET, trifluoromethylphenyl end capped material (TFP-TBT) shows n-channel behaviour whereas butoxyphenyl end capped material (BOP-TBT) shows p-channel behaviour. Density functional theory calculations correlated with shifting of HOMO-LUMO energy levels with respect to end capping groups. Vacuum processed OFET of these materials have shown highest hole carrier mobility of 0.02 cm2/Vs and electron carrier mobility of 0.004 cm2/Vs, respectively using Si/SiO2 substrate. By keeping the central D-A-D segment and just by tuning end capping groups gives both p- and n-channel organic semiconductors which can be prepared in a single step using straightforward synthesis.

Studies of Li-Air Cells Utilizing Dimethyl Sulfoxide-Based Electrolyte

Dimethyl Sulfoxide (DMSO) was evaluated as a practical solvent for the rechargeable lithium air battery. Redox characteristics of the dissolved oxygen and its reduction products in the presence of lithium hexafluorophosphate (LiPF6) supporting electrolyte were studied via cyclic, rotating disk (RDE) and ring-disk (RRDE) electrode voltammetry. The DMSO medium facilitates reversible reduction and oxidation processes in contrast to other solvent-based electrolytes studied. Galvanostatic discharge-charge cycling of the Li-O2 cells has shown characteristics of rechargeability expected from voltammetric studies. Multiple high-efficiency discharge-charge cycles are possible if the depth of discharge of the carbon cathode is limited to avoid excessive passivation by the discharge products. The discharge voltage of this Li-O2 cell is higher than cells assembled with other non-aqueous organic electrolytes, an attribute ascribed to the stability of superoxide (O2−), the one-electron reduction product of oxygen.

Double Layer Energy Storage in Graphene - a Study

An alternate energy storage device for high power applications are supercapacitors. They store energy either by pure electrostatic charge accumulation in the electrochemical double layer or as pseudo capacitance from fast reversible oxidation reduction process. However, they have low energy density. The electrodes in the Electrochemical Double Layer Capacitors (EDLC) are made of high surface area carbon. The carbon that can be used range from activated carbon to Graphene, with varying particle size, surface area, pore size and pore distribution. The main emphasis in the development of EDLCs is fabrication of electrodes having high surface area which would enhance the storage density of the EDLC. The EDLCs are assembled with different electrolytes which determine the operational voltage. Solid electrolytes can also be used as electrolyte and have an advantage in that we can avoid electrolyte leaks and are easy to handle. This would improve the reliability. They can also be shaped and sized to suit the application. The perflurosulfonic acid polymer as electrolyte has been used by various groups for EDLC application. The perflurosulfonic acid polymer possesses high ionic conductivity, good thermal stability, adequate mechanical strength and excellent chemical stability. The EDLCs, which are based on high-surface area carbon materials, utilize the capacitance arising from a purely non-Faradaic charge separation at an electrode/electrolyte interface. Carbon is widely used for many practical applications, especially for the adsorption of ions and molecules, as catalyst supports and electrode materials. The chemical characteristics of carbon determine the performance in all these applications. It is now possible to synthesize one-, two-, or three-dimensional (1-, 2-, or 3-D) carbons. Thus, carbon materials are very suitable candidates for super capacitor electrodes. We can overcome some of the problems in activated carbon like varying micro or meso pores, poor ion mobility due to varying pore distribution, low electrical conductivity, by using Graphene. Many forms of Graphene have been used by various groups. Graphene nanoplates (GNP), with narrow mesopore distribution have been effectively used to enhance charge storage performance. It has been found that graphene shows smaller decrease in storage capacity with increasing scan rate.

Tetrathiafulvalene-based lanthanide coordination complexes: Synthesis, crystal structure, optical and electrochemical characterization

The explorative lanthanide coordination chemistry of 4′,5′-bis-(propylthio)tetrathiafulvenyl[ i ]dipyrido[3,2- a :2′,3′- c ]phenazine (TTF-dppz) is described. Thereby, four new Ln(III) complexes, [Ln(NO 3 ) 3 (TTF-dppz) 2 ] with Ln(III) = Nd ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), have been prepared and characterized. An X-ray crystallographic study of [Gd(NO 3 ) 3 (TTF-dppz) 2 ] ( 3 ) shows that the Gd(III) ion is coordinated to six oxygen atoms from three bidentate nitrate ligands and four nitrogen atoms from two bidentate TTF-dppz molecules forming a distorted bicapped square antiprism coordination geometry. The UV-vis spectra of the four Ln(III) complexes show very strong absorption bands in the UV region consistent with ligand centred electronic π-π* transitions and an intense broad absorption band in the visible region corresponding to a spin-allowed electronic π-π* 1 ILCT transition from the TTF-dppz ligand. Upon coordination, the 1 ILCT band of the free TTF-dppz ligand is bathochromically shifted. The electrochemical studies reveal that all complexes undergo two reversible oxidation and one (quasi)reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the dppz unit, respectively. Moreover, the magnetic properties of complexes 3 and 4 are discussed.

Multilevel Resistive Switching in Planar Graphene/SiO2 Nanogap Structures

We report a planar graphene/SiO(2) nanogap structure for multilevel resistive switching. Nanosized gaps created on a SiO(2) substrate by electrical breakdown of nanographene electrodes were used as channels for resistive switching. Two-terminal devices exhibited excellent memory characteristics with good endurance up to 10(4) cycles, long retention time more than 10(5) s, and fast switching speed down to 500 ns. At least five conduction states with reliability and reproducibility were demonstrated in these memory devices. The mechanism of the resistance switching effect was attributed to a reversible thermal-assisted reduction and oxidation process that occurred at the breakdown region of the SiO(2) substrate. In addition, the uniform and wafer-size nanographene films with controlled layer thickness and electrical resistivity were grown directly on SiO(2) substrates for scalable device fabrications, making it attractive for developing high-density and low-cost nonvolatile memories.

Remarkable Sensitivity of the Electrochemical Reduction of Benzophenone to Proton Availability in Ionic Liquids

The reduction of benzophenone was investigated in five different ionic liquids by using transient cyclic voltammetry, near steady-state voltammetry, and numerical simulation. Two reversible, well-resolved one-electron-reduction processes were observed in dry (≤20 ppm water, ca. 1 mM)) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpyrd][NTf(2)]) and 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide ([Bmpipd][NTf(2)]), which did not contain any readily available proton source. Upon addition of water, the second process became chemically irreversible and shifted to a more positive potential by approximately 600 mV; moreover, the two reduction processes merged into a single two-electron proton-coupled process when about 0.6 M H(2)O was present. This large dependence of potential on water content, which was not observed in molecular solvents (electrolyte), was explained by a reaction mechanism that incorporated protonation and hydrogen-bonding interactions of the benzophenone dianion with as many as seven water molecules. In the three imidazolium-based ionic liquids used herein, the first benzophenone-reduction process was again reversible, whilst the second reduction process became chemically irreversible owing to the availability of the C2-H imidazolium protons in these ionic liquids. The reversible potentials for benzophenone reduction were remarkably independent of the identity of the ionic liquids, thereby implying either weak interactions with the ionic liquids or relatively insignificant differences in the levels of ion-pairing. Thus, the magnitude of the separation of the potentials of the reversible first and irreversible second reduction processes mainly reflected the proton availability from either the ionic liquid itself or from adventitious water. Consequently, voltammetric reduction of benzophenone provides a sensitive tool for the determination of proton availability in ionic liquids.

Intramolecular π-stacking in cationic iridium(iii) complexes with a triazole–pyridine type ancillary ligand: synthesis, photophysics, electrochemistry properties and piezochromic behavior

To make Ir(III)-based complexes potentially multifunctional materials, two new cationic Ir(III) complexes with a 2-(5-phenyl-2-phenyl-2H-1,2,4-triazol-3-yl)pyridine (Phtz) ancillary ligand were designed and synthesized. By introducing the pendant phenyl ring into the ancillary ligand, the two complexes possess desired intramolecular π–π stacking between the pendant phenyl ring of the Phtz ligand and one of the phenyl rings of the cyclometalated ligand, which renders the complexes more stable. Density functional theory calculation indicates that the intramolecular π–π interactions in both complexes can reduce the degradation reaction in metal-centered (3MC) states to some extent, which further implies their stability. With these results in combination with their reversible oxidation and reduction processes as well as excellent photophysical properties, the stable light-emitting cells (LECs) would be expected. Furthermore, the two synthesized complexes exhibit reversible piezochromism. Their emission color can be smartly switched by grinding and heating, which is visible to the naked eye. In light of our experimental results, the present piezochromic behavior is due to interconversion between crystalline and amorphous states.

Side-chain selenium-containing amphiphilic block copolymers: redox-controlled self-assembly and disassembly

In this paper we report the synthesis and study of a series of side-chain selenium-containing amphiphilic poly(ethylene oxide-b-acrylic acid) block copolymers PEO-b-PAA-Se. These block copolymers can self-assemble in aqueous solution and form spherical micellar aggregates. The selenide group of PEO-b-PAA-Se can change into hydrophilic selenoxide under mild oxidation of 0.1% hydrogen peroxide, leading to the disassembly of the spherical micellar aggregates. Small compounds like Nile Red can be encapsulated into the micellar aggregates and show fast release upon the addition of 0.1% hydrogen peroxide. More interestingly, the oxidation state of selenoxide can be reversed to selenide under reduction of Vitamin C, thus recovering the spherical aggregates. The reversible oxidation and reduction process shows good reversibility and can be repeated at least 7 times. It is hoped that this reversible redox controlled system may function as nanocontainers for potential application in the areas such as responsive drug delivery and anti-oxidation studies.

Synthesis and structural characterisation of (aryl-BIAN)copper(i) complexes and their application as catalysts for the cycloaddition of azides and alkynes

A series of Ar-BIAN-based copper(I) complexes (where Ar-BIAN = bis(aryl)acenaphthenequinonediimine) were synthesised and characterised by (1)H and (13)C NMR spectroscopies, FT-IR spectroscopy, MALDI-TOF-MS spectrometry, cyclic voltammetry and single crystal X-ray diffraction. The bis-chelated complexes of general formula [Cu(Ar-BIAN)(2)]BF(4) (where Ar = C(6)H(5) (1), 4-iPrC(6)H(4) (3), 2-iPrC(6)H(4) (4)) were prepared by reaction of [Cu(NCMe)(4)]BF(4) with two equivalents of the corresponding Ar-BIAN ligands, in dichloromethane, while the mono-chelated complexes of the type [Cu(Ar-BIAN)L(2)]BF(4) (where Ar = 2,6-iPr(2)C(6)H(3), L = PhCN (6); Ar = 4-iPrC(6)H(4), L = PPh(3) (7)) were readily accessible by treatment of [Cu(NCR)(4)]BF(4) (R = Me, Ph) with one equivalent of the corresponding Ar-BIAN ligands in the absence or presence of two equivalents of PPh(3), in the same solvent. The structures of complexes 3, 4, 6 and 7 were obtained by single crystal X-ray diffraction, showing distorted tetrahedral geometries around the copper centres in all cases. The electrochemical studies of these complexes and of the already reported [Cu(2,4,6-Me(3)C(6)H(2)-BIAN)(2)]BF(4) (2) and [Cu(2,6-iPr(2)C(6)H(3)-BIAN)(NCMe)(2)] (5), demonstrated that the bis-chelated complexes 1-4 undergo a reversible one-electron reduction or oxidation processes on copper, while the mono-chelated complexes 5-7 show a partially reversible oxidation and an irreversible reduction feature. Both kinds of (Ar-BIAN)copper(I) complexes are active catalysts for the copper(I)-catalysed azide-alkyne cycloaddition reaction (CuAAC). Complex 7, bearing PPh(3) ligands, exhibits the highest catalytic activity, which is comparable with that of the typical CuSO(4)-sodium ascorbate catalyst system.

Polarographic Determination and Antimicrobial Activity of Cu(II) Complex with 4-Chlorobenzylidene-4-aminoacetanilide

The electrochemical behaviour of the complex of Cu(II) with 4-chlorobenzylidene-4-aminoacetanilide (CAA) was studied. It was observed that CAA forms 1:1 complex with Cu(II) in between pH 6.5 to 7.1. It was found that the reduction process of Cu(II)- CAA complex is two electron reversible reduction process at D.M.E. The logarithm value of stability constant of Cu(II)-4-Chlorobenzylidene-4-aminoacetanilide (CAA) complex has been found to be 4.85.The redox properties of the complex was extensively investigated by electrochemical method using cyclic voltammetry (CV).The Cu(II) complexes exhibited quasi-reversible single electron transfer process.The Schiff base and its complex has been screened for theirin-vitroantibacterial (Escherichiacoli,Staphylococcus aureus,Vibrio choleraeandBacillus subtilis) and antifungal (Aspergillus nigerandPenicillium liliacinum) activities by minimum inhibitory concentration (MIC) method.

Dicyanovinylene-Substituted Selenophene–Thiophene Co-oligomers for Small-Molecule Organic Solar Cells

We report on the design, synthesis, and characterization of a series of terminal dicyanovinylene-substituted quinquechalcogenophenes as light-harvesting small-molecule donor materials for organic solar cells. The spectroscopic, electrochemical, and thermal properties of these pentamers were investigated. The replacement of thiophene unit(s) by selenophene(s) results in a bathochromic shift of the longest wavelength absorption band with concomitant increase of the molar extinction coefficient. Cyclic voltammetry measurements revealed fully reversible oxidation and irreversible reduction processes. The highest occupied and lowest unoccupied molecular orbital (HOMO/LUMO) energy levels were determined from electrochemical measurements and lie in the range of −5.6 and −3.8 eV. Vacuum-deposited bulk-heterojunction solar cells fabricated with the novel chalcogenophenes as donor and C60 as acceptor displayed high open-circuit voltages of up to 1 V, short-circuit currents close to 8 mA·cm–2, and power conversion efficiencies over 3%.

Optical properties and electronic structure of terminal group-perturbed ethynyl-linked dendrimers

Three ethynyl-linked dendrimers with terminal carbazole, namely the electronic donor–acceptor compounds 1–3, the symmetric compound 9-(3-(2-(1-(2-(3-(9Hcarbazol-9-yl)-9-p-tolyl-9H-carbazol-6-yl)ethynyl)pyren-6-yl)ethynyl)-9-p-tolyl-9H-carbazol-6-yl)-9H-carbazole ( 1), the unsymmetric compounds 6-pyren-1-ylethynyl-9- p-tolyl-9 H-[3,9′]bicarbazolyl ( 2) and 3,6-di- tert-butyl-9-(4-pyren-1-ylethynyl-phenyl)- 9H-carbazole ( 3), respectively, were well investigated by experimental and theoretic methods. Good reversible oxidation and reduction processes of these compounds were observed, and the corresponding HOMO and LUMO levels could be well tuned by the different terminal group, which was proved by the theoretical calculation. In addition, they showed bright blue-green emission in dichloromethane solution and in the solid state, and exhibited efficient solvatochromism, suggesting that their electron transition may be considered as π–π* transition, charge–transfer transition and the coeffect of the former two, respectively.

An Unsymmetrical Trinickel Metal Complex with 4-Sulfobenzoate Axial Ligand: [Ni3(dpa)4(4-sb)(H2O)]×3H2O

An unsymmetrical trinickel metal complex, [Ni3(dpa)4(4-sb)(H2O)]×3H2O (1), where dpa is a 2,2’-dipyridylamine anion and 4-sb is 4-sulfobenzoate dianion, was synthesized and characterized by X-ray crystallography, IR, elemental analysis, fluorescence, and cyclic voltammetry. The molecular structure of 1 is a cluster with a linear trimer. The extended structure is a 3D architecture assembled by hydrogen bonds. The 4-sulfobenzoate axial replacement leads to the change of Ni-Ni distances, the shift of the fluorescence emission, and the reversible one-electron reduction process without oxidation process.

Synthesis, Crystal Structure and Electrochemical Property of New Rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)bis(azido)cobalt(III) Nitrate Methanol Solvate Complex

The new cobalt compound, [Co(C16H35N10]+(NO3)−·CH3OH (1), have been synthesized and characterized. It’s structure and electrochemical property were investigated using single-crystal X-ray diffraction and cyclic voltammetry in solutions of dimethyl sulfoxide (DMSO) and methanol (CH3OH). The X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic space group P21/c with a = 9.8339 (10) A, b = 16.4048 (17) A, c = 15.3628 (16) A, β = 104.96 (9)° and Z = 4. The complex 1 consists of one [Co(C16H35N10)]+ cation, one NO3 − anions and one solvent CH3OH molecule. The metal center of complex 1 is six-coordinated, with the four nitrogens of the macrocycle defining an equatorial plane and two axially ligated [N3]− ions completing the cobalt coordination sphere. Moreover, hydrogen bonds of O–H⋯N, O–H⋯O and N–H⋯O and static force connect two components of the compound and maintain the crystal structure. Additionally, in situ spectro-electrochemical measurements support Co(III)/Co(II) reversible reduction processes with the observation of the corresponding spectral changes with the applied potentials E app = −1.5 and 0.5 V. The results obtained by the method are in agreement with those by the CV methods. The paper is about synthesis, crystal structure and electrochemical property of a new complex.

‘Double redox-activity’ in azobenzene-quinonoid palladium(ii) complexes: a combined structural, electrochemical and spectroscopic study

Reactions of [(az(-H))Pd(μ-Cl)(2)Pd(az(-H))] (az = azobenzene) with the zwitterionic, p-benzoquinonemonoimine-type ligands 4-(n-butylamino)-6(n-butylimino)-3-oxocyclohexa-1,4-dien-1-olate (Q(1)) or 4-(isopropylamino)-6(isopropylimino)-3-oxocyclohexa-1,4-dien-1-olate) (Q(2)) in the presence of a base leads to the formation of the mononuclear complexes [(az(-H))Pd(Q(1)(-H))] (1) and [(az(-H))Pd(Q(2)(-H))] (2) respectively. Structural characterization of 2 shows an almost square planar coordination geometry around the Pd(II) centre, a short Pd-C bond, a slight elongation of the N=N double bond of the az(-H) ligand and localization of the double bonds within the Q(2)(-H) ligand. Additionally, intermolecular N-H-O interactions exist between the uncoordinated N-H and O groups of two different molecules. Cyclic voltammetry of the complexes reveals an irreversible oxidation and two reversible reduction processes. A combination of electrochemical and UV-vis-NIR and EPR spectroelectrochemical studies are used to show that both coordinated ligands participate successively in the redox processes, thus revealing their non-innocent character.

Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes

The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono- and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(μ-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac(-) anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred π-π* transitions and an intense broad band in the visible region corresponding to a spin-allowed π-π* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively.

Thiophene–benzothiadiazole–thiophene (D–A–D) based polymers: effect of donor/acceptor moieties adjacent to D–A–D segment on photophysical and photovoltaic properties

New push–pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31 100 and 8400 g mol−1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10−4 cm2 V−1 s−1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1 : 4 ratio, exhibiting a short-circuit current of 7.27 mA cm−2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm−2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm−2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

Effect of substituents on redox, spectroscopic and structural properties of conjugated diaryltetrazines—a combined experimental and theoretical study

Two series of new soluble conjugated compounds containing tetrazine central ring have been synthesized. The three-ring compounds have been synthesized by the reaction of aryl cyanide (where aryl = thienyl, alkylthienyl, phenyl or pyridyl) with hydrazine followed by oxidation of the intermediate product with diethyl azodicarboxylate. The five-ring compounds have been prepared using two pathways: (i) reaction of 5-cyano-2,2'-bithiophene (or its alkyl derivative) with hydrazine; (ii) via Suzuki or Stille coupling of 3,6-bis(5-bromo-2-thienyl)-1,2,4,5-tetrazine with a stannyl or boronate derivative of alkylthiophene. UV-vis spectroscopic properties of the synthesized compounds are strongly dependent on the nature of the aryl group, the position of the solubilizing substituent and the length of the molecule, showing the highest bathochromic shift (λ(max) > 440 nm) for five-ring compounds with alkyl groups attached to C(α) carbon in the terminal thienyl ring. An excellent linear correlation has been found for spectroscopically determined and theoretically calculated (TD-B3LYP/6-31G*) excitation energies. With the exception of dipyridyl derivative, the calculated lowest unoccupied molecular orbital (LUMO) level of the investigated molecules changes within a narrow range (from -2.63 to -2.41 eV), in line with the electrochemical data, which show a reversible reduction process with the redox potential varying from -1.23 V to -1.33 V (vs. Fc/Fc(+)). The electrochemically determined positions of the LUMO levels are consistently lower by 0.9 to 1.2 eV with respect to the calculated ones. All molecules readily crystallize. Single crystal studies of 3,6-bis(2,2'-bithien-5-yl)-1,2,4,5-tetrazine show that it crystallizes in a P2(1)/c space group whose structural arrangement is not very favorable to the charge carriers flow within the crystal. Powder diffraction studies of other derivatives have shown that their structural organization is sensitive to the position of the solubilizing substituent. In particular, the presence of alkyl groups attached to C(α) carbon in the terminal thienyl ring promotes the formation of a lamellar-type supramolecular organization.