Foliar Application of Benzothiadiazole and Salicylic Acid to Combat Sheath Blight Disease of Rice

A field study was undertaken to ascertain the effects of elicitors viz. benzothiadiazole （BTH） and salicylic acid （SA） on defense related enzymes viz. peroxidase, phenylalanine ammonia lyase, superoxide dismutase, chitinase and 13-1,3-glucanase, and phenols in rice （Pusa Basmati I） plants. First foliar spray of BTH （50 mg/kg） and SA （50 mg/kg） was done at the maximum tillering stage and inoculation with Rhizoctonia solani was carried 24 h after elicitor treatment. Elicitors were further sprayed at every growth stage. Time course analysis showed peak accumulation of defense related enzymes and phenols in the rice leaves treated with BTH and SA, and accumulation was the highest at the flowering stage. Higher enzymatic activity was observed in elicitor treated plants inoculated with R. solani. Compared to the untreated control plants, application of elicitors before R. solani inoculation significantly elicited the defense related enzymes and phenols. Moreover, application of elicitors had a positive effect on yield and disease reduction. It is suggested that pretreatment of rice leaves with BTH and SA could be used to enhance the level of protection against sheath blight and to improve rice yield in the fields.

Fluorine-Mediated Benzothiadiazole Derivatives for Second-Order Nonlinear Optics

With increasing research interests in the field of light-matter interactions,various methods have been developed for regulating nonlinear optical(NLO)materials.However,the design and synthesis of organic molecular materials for second-order nonlinear optics remain a great challenge because of the strict requirement of the materials to possess a noncentrosymmetric structure.In this work,two benzothiadiazole(BTD)derivatives referred to as BTD-H and BTD-F were synthesized,and their NLO properties in the crystalline states were studied.It was found that introducing fluorine into the BTD backbone effectively tuned the crystal packing styles of BTD derivatives to a noncentrosymmetric system for effective second-order NLO responses.Such a strategy to induce the noncentrosymmetric structure by introducing the fluorine atoms and halogen interactions may provide guidance for future engineering of organic NLO molecular materials.

Benzothiadiazole-based materials for organic solar cells

The past few years have witnessed power conversion efficiency(PCE)of organic solar cells(OSCs)skyrocketing to the value of 20%due to the outstanding advantages of organic photoactive materials.The latter,which consist of donor and acceptor materials,indeed play important roles in OSCs,and particularly one building block has attracted considerable research attention,namely benzothiadiazole(BT).The diversity of OSCs based on the BT structure have indeed sprung up,and the progressive increase in PCE values is more than just eye-catching since it heralds a renewal and bright future of OSCs.This review analyzes significant studies that have led to these remarkable progresses and focuses on the most effective BT small-molecules and BT polymers for OSC reported in the last decades.The pivotal structure-property relationships,donor-acceptor matching criteria,and morphology control approaches are gathered and discussed in this paper.Lastly,we summarize the remaining challenges and offer a personal perspective on the future advance and improvement of OSCs.

Structure-Property Relationship of Conjugated Polymers Utilizing Isomerized Fused Benzothiadiazole-Based Building Blocks

Only a few fused benzothiadizole(BTz)based conjugated polymers have been applied in organic field-effect transistors(OFETs),and their performances were low,mainly due to the lack of available building blocks and in-depth study of the relationship between structure and performance.Herein,we report two isomeric fused BTz-based building blocks(M1 and M2)and their copolymers PBTzVBTz-T and PBTzVBTz-TT,PTVT-T and PTVT-TT.DFT study showed all polymers had nearly planar backbone geometries,and PBTzVBTz-TT exhibited the most linear backbone.PTVT-T and PTVT-TT exhibited red-shift absorption spectra and deeper LUMO level than those of PBTzVBTz-T and PBTzVBTz-TT.Thin film microstructure study demonstrated PBTzVBTz-TT and PTVT-TT had edge-on molecular orientation,while the others had the mixed molecular orientation of edge-on and face-on.Furthermore,PBTzVBTz-TT had the longest coherence length in thin film.All these features of PBTzVBTz-TT resulted in its highest carrier mobility of 0.1 cm^(2)·V^(–1)·s^(–1) among these polymers.

Benzothiadiazole-based Conjugated Polymers for Organic Solar Cells

Benzothiadiazole(BT)is an electron-deficient unit with fused aromatic core,which can be used to construct conjugated polymers for application in organic solar cells(OSCs).In the past twenty years,huge numbers of conjugated polymers based on BT unit have been developed,focusing on the backbone engineering(such as by using different copolymerized building blocks),side chain engineering(such as by using linear or branch side units),using heteroatoms(such as F,O and S atoms,and CN group),etc.These modifications enable BT-polymers to exhibit distinct absorption spectra(with onset varied from 600 nm to 1000 nm),different frontier energy levels and crystallinities.As a consequence,BT-polymers have gained much attention in recent years,and can be simultaneously used as electron donor and electron acceptor in OSCs,providing the power conversion efficiencies(PCEs)over 18%and 14%in non-fullerene and all-polymer OSCs.In this article,we provide an overview of BT-polymers for OSCs,from donor to acceptor,via selecting some typical BT-polymers in different periods.We hope that the summary in this article can invoke the interest to study the BT-polymers toward high performance OSCs,especially with thick active layers that can be potentially used in large-area devices.

Vinyl-functionalized multicolor benzothiadiazoles: design,synthesis, crystal structures and mechanically-responsive performance

Benzothiadiazole(BTD) has been extensively used as a building block in optical materials. In this work, a class of π-conjugated BTD-based luminogens BTD-685, BTD-580, BTD-675 and BTD-565 were designed by varying donor units and facilely synthesized by Heck coupling reaction. It was found that their emission in solid state covered the regio from orange, red to near infrared fluorescence. Investigation on photo-physical property manifested that they had strong solvatochromic behavior except symmetric 2-vinylpyridine substituted BTD-565. Crystal X-ray diffraction analysis revealed that they involved in multi weak intermolecular interactions. And loose molecular packing implied that they can be easily rearranged under external force stimuli.Indeed, all compounds showed reversible mechanically-responsive behavior in solid state. Interestingly, the vinylpyridinecontaining BTD-565 exhibited hypochromatic mechanochromic behavior, whereas others showed bathochromic mechanochromism behavior. It was worth mentioning that BTD-675 had self-recovery behavior after grinding. The powder X-ray diffraction study showed that these chromic processes may be mainly attributed to the reversible morphological changes between crystalline and amorphous phase upon grinding or fuming. These observations suggested that the vinyl-functionalized benzothiadiazoles can be considered as a type of excellent candidates in mechanically-responsive chromic materials.

Efficient solar cells based on cosensitizing porphyrin dyes containing a wrapped donor, a wrapped π-framework and a substituted benzothiadiazole unit

Three new porphyrin dyes XW45-XW47 have been synthesized employing a dialkoxy-wrapped phenothiazine donor, a tetraalkoxy-wrapped porphyrin π-framework, a benzothiadiazole(BTD)-based auxiliary acceptor, and an anchoring benzoic acid group. On the basis of our previously reported dye XW36, XW45 was synthesized by introducing a BTD unit to broaden the absorption spectrum, further introducing a hexyl-substituent into the BTD unit afforded XW46, and an additional fluorine atom was introduced to the carboxyphenyl acceptor to afford XW47. As expected, the BTD unit obviously broadens and red-shifts the absorption threshold of XW45-XW47 to ca.750 nm. Dye-sensitized solar cells(DSSCs) were fabricated based on a cobalt electrolyte using chenodeoxycholic acid(CDCA) as the coadsorbent. Under full sun illumination, XW45 exhibits an efficiency of 9.73%, which is slightly lower than that of 10.19% obtained for the reference dye SM315. By contrast, XW46 and XW47 show higher efficiencies than SM315 owing to the improved anti-aggregation ability associated with the hexyl group on the BTD unit and better ICT effect induced by the fluorine atom on the carboxyphenyl unit. Thus, XW47 exhibits the highest efficiency of 10.41% among the porphyrin dyes. Furthermore, PT-C6 was used as the cosensitizer to improve the light harvesting ability and efficiencies of the cells due to its broad absorption within 350–560 nm. Thus, high efficiencies of 10.32%, 11.38% and 10.90% were achieved for the cosensitized solar cells based on XW45–XW47, respectively, owing to the obviously enhanced photocurrent density(JSC). In addition, under 30% full sun illumination, XW46+PT-C6 exhibits a high efficiency of 13.08%. These results give an effective method for building high performance DSSCs through the cosensitization of porphyrin dyes containing a wrapped donor, a wrapped porphyrin framework and a properly substituted auxiliary benzothiadiazole unit.

Dithienocarbazole- and benzothiadiazole-based donor-acceptor conjugated polymers for bulk heterojunction polymer solar cells

Donor-acceptor （D-A）-conjugated polymers P（BT-C1） and P（BT-C2）, with dithieno[2,3-b;7,6-b]carbazole （C1） or dithi- eno[3,2-b;6,7-b]carbazole （C2） as D-unit and benzothiadiazole （BT） as A-unit, were synthesized. The optical bandgaps of the polymers are similar （1.84 and 1.88 eV, respectively）. The structures of donor units noticeably influence the energy levels and backbone curvature of the polymers. P（BT-C1） shows a large backbone curvature; its highest occupied molecular orbital （HOMO） energy level is -5.18 eV, whereas P（BT-C2） displays a pseudo-straight backbone and has a HOMO energy level of -5.37 eV. The hole mobilities of the polymers without thermal annealing are 1.9×10^-3 and 2.7×10^-3 cm^2 V-1 s^-1 for P（BT-C1） and P（BT-C2）, respectively, as measured by organic thin-film transistors （OTFTs）. Polymer solar cells using P（BT-C1） and P（BT-C2） as the donor and phenyl-Cyl-butyric acid methyl ester （PCyLBM） as the acceptor were fabricated. Power conversion efficiencies （PCEs） of 4.9% and 5.0% were achieved for P（BT-C1） and P（BT-C2）, respectively. The devices based on P（BT-C2） exhibited a higher Voc due to the deeper HOMO level of the polymer, which led to a slightly higher PCE.

Synthesis of two-dimensional π-conjugated polymers pendent with benzothiadiazole and naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole moieties for polymer solar cells

Four new 2D donor–acceptor conjugated polymers were designed and synthesized.These new polymers comprised fluorenealt-triphenylamine or carbazole-alt-triphenylamine as the backbones,and pendants with 2,1,3-benzothiadiazole(BT)or naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole(NT)in a triphenylamine unit as the side groups.By changing the acceptor BT for a stronger electron-withdrawing unit of NT moiety in the side chain,the energy levels,absorption spectra,band gaps,and charge-transport abilities of the resultant polymers could be effectively tuned.Bulk heterojunction solar cells with these polymers as the electron donors and(6,6)-phenyl-C71-butyric acid methyl ester as the electron acceptor exhibited high open-circuit voltage(more than 0.8 e V).The power conversion efficiency can be improved from 1.37%to 3.52%by replacing the BT with an NT moiety,which indicates that introducing NT as the side-chain building block can be an effective strategy to construct efficient 2D conjugated polymers for PSCs.

A study on JA-and BTH-induced resistance of Rosa rugosa‘Plena’to powdery mildew(Sphaerotheca pannosa)

Different concentrations of jasmonic acid(JA)and benzothiadiazole(BTH) were sprayed on 2-year-old Rosa rugosa‘Plena’ seedlings. The induced resistance of JA and BTH to Sphaerotheca pannosa(Wallr.) and the changes of their related physiological indices were investigated. Results showed that JA and BTH treatments had inhibitory impacts on S. pannosa infection. The optimal concentration of JA and BTH was 0.5 mmol/L for the disease-resistance induction of the leaves, its inductive effect was up to 66.36% for BTH and 54.49% for JA. Our results confirmed that exogenous JA and BTH significantly improved R. rugose ‘Plena’ resistance to S. pannosa. When treated with JA and BTH, activities of the three defense enzymes(POD, PPO, and PAL) increased significantly.Contents of total phenolics, flavonoids, and lignin also increased significantly. It is inferred from these results that exogenous JA and BTH could improve the resistance of R.rugose ‘Plena’ to S. pannosa through enhancing activities of the defensive enzymes and accumulation of secondary metabolites in the leaves.

Construction and Analysis of SSH-cDNA Library from Leaves of Susceptible Rubber Clone Resistant to Powdery Mildew Induced by BTH

To understand the mechanism of benzothiadiazole (BTH)-induced susceptible rubber clone resistance to powdery mildew on gene level, a differentially expressed cDNA library was constructed by suppression subtractive hybridization (SSH) with rubber Reyan 7-33-97 clone. The constructed cDNA library was high integrity through detection of the critical processes of SSH, such as efficiency of adaptor connection, subtraction and conversion, as well as the type of recombinant genes. The positive rate was 99% after identification with random 400 white spots. The size of the cDNA clone inserted fragments was various but most in 400 bp - 1000 bp. There were 23 cDNA sequences matching the function of energy and basic metabolism, signal transduction, membrane and transport, secondary metabolism and so on after detection of the 42 positive clone sequences selected randomly from the cDNA library and comparison on nucleic acid sequences in Genbank. 7 ESTs were logged in Genbank and accession numbers were GW873071 and GW874604- GW874610. The results implicated that BTH could effectively induced rubber tree resistance to powdery mildew through increasing expresses of defense-related genes in leaves of rubber tree susceptible clone. It should provide a new approach for rubber disease management.

Synthesis of Long-Chain Oligomeric Donor and Acceptors via Direct Arylation for Organic Solar Cells

The rapid synthesis of structurally complicated electron donors&acceptors still remains a major challenge in organic solar cells(OSC).In this work,we developed a highly efficient strategy to access long-chain oligomeric donor and acceptors for OSC applications.A series of cyclopentadithiophene(CPDT)and benzothiadiazole(BT)-basedπ-conjugated oligomers,i.e.,three oligomeric acceptors(BTDT)n-IC(n=1—3)and one long-chain oligomeric donor(BTDT)4-RD,are facilely synthesized by an atom-and step-economical,and labor-saving direct C—H arylation(DACH)reaction(i.e.,C—H/C—Br cross coupling).Note that(BTDT)4-RD involving five CPDT,four BT and two rhodamine(RD)building blocks is the longest oligomeric donor in the fullerene-free OSC devices ever reported.The dependence of the structure-property-performance correlation of(BTDT)n-IC(n=1—3)and(BTDT)4-RD on theπ-conjugation lengths is thoroughly investigated by opto-electrochemical measurements,bulk heterojunction(BHJ)OSC devices and microscopies.The(BTDT)1-IC:PBDB-T and(BTDT)4-RD:Y6 BHJs achieve power conversion efficiencies of 9.14%and 4.51%,respectively.Our findings demonstrate that DACH reaction is a powerful tool to tune the opto-electronic properties and device performances by regulating the lengths ofπ-conjugated oligomers with varied numbers of repeating units.

Synthesis and Photovoltaic Properties of Poly（5,6-bis（octyloxy）-4,7- di（thiophen-2-yl）benzo-[c] [l,2,5]-thiadiazole-9,9-dioctvlfluorene）

A donor-acceptor type conjugated polymer poly（5,6-bis（octyloxy）-4,7-di（thiophen-2-yl）benzo-[c] [1,2,5]- thiadiazole-9,9-dioctylfluorene） （POTBTF） based on octyloxy-containing benzothiadiazole （OTBT） and octyl- containing fluorine （F） was synthesized by Suzuki coupling reaction. The polymer possesses a narrow bandgap and strong light harvesting ability with excellent thermal stability and reasonable solubility. POTBTF exhibited a broad absorption from 300 to 600 nm with an absorption peak at 543.8 nm. The power conversion efficiency of the polymer solar cell based on POTBTF/PC71BM （1：3, w/w） reached 1.77% with a short-circuit current density of 6.69 mA/cm2, an open-circuit voltage of 0.71 V, and a fill factor of 0.374 under AM 1.5 G irradiation （100 mW/cm2） without annealing or any additives. The results indicate that introducing long alkoxy side chains into benzothiadiazole would not only improve the solubility of the polymers but also maintain the planarity of molecule conformation, and therefore, enhance the performance of photovoltaic devices.

Synthesis and Characterization of Novel Organic Semiconductors

1 Results Development of new organic semiconductors for use in low-cost,large-area applications is very important for growth of the organic electronic industry.Existing non-polymer based organic semiconductors can be roughly classified into linear,star-shaped,branched or lamellar molecules on the basis of their shape[1]. Generally hole (p-type) and electron (n-type) transporting semiconductors have been prepared from electron donating and accepting π-systems respectively[2]. These materials can be used ...

Effective design of A-D-A small molecules for high performance organic solar cells via F atom substitution and thiophene bridge

Three novel small molecules with acceptor-donor-acceptor(A-D-A) configuration,SBDT1,SBDT2 and SBDT3,where 4,8-bis(octyloxy)benzo[1,2-b:4,5-b’]dithiophene(BDT) as the electron-donating core connecting to thiophene-substituted benzothiadiazole(BT) as electron-withdrawing are reported.The effects of fluorine atoms on the photophysical properties by introducing different fluorine atoms into the benzothiadiazole unit were investigated.These SBDTs exhibit good thermal stability,excellent panchromatic absorption in solution and film.SBDT2 and SBDT3 with fluorine-substituted BT possess a relatively deeper the highest occupied molecular orbital(HOMO).These A-D-A type molecules were treated as donor and PC71 BM as acceptor in bulk heterojunction(BHJ) small-molecule organic solar cells(SMOSCs).Among them,device based on SBDT2 gave the best device performance with a PCE of 5.06%with Jsc of 10.56 mA/cm^2,Voc of 0.85 V,fill factor(FF) of 56.4%.These studies indicate that proper incorporation of fluorine atoms is an effective way to increase the efficiency of organic solar cells.