Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions

• Karolis Leitonas,
• Brigita Vigante,
• Dmytro Volyniuk,
• Audrius Bucinskas,
• Pavels Dimitrijevs,
• Sindija Lapcinska,
• Pavel Arsenyan and
• Juozas Vidas Grazulevicius

Beilstein J. Org. Chem. 2023, 19, 1867–1880, doi:10.3762/bjoc.19.139

• compound 4 with 4,4’-diethynylbiphenyl and 5,5’-diethynyl-3,3’-dihexyl-2,2’-bithiophene, respectively. Finally, the snowflake-shaped compound 9 bearing three dicyanopyridyl moieties was constructed by the treatment of 1,3,5-triethynylbenzene with 3 equiv of 4. The structural identity and purity of

• of REF fragments in the structures of compounds 6–9 does not have any strong effect on the positions of their absorption spectra. As a result, similar optical band gaps (Egopt.) of 2.74–2.8 eV were obtained for 6–9. It should be noted that the 5,5’-diethynyl-3,3’-dihexyl-2,2’-bithiophene bridge of

• ’-(((3,3’-Dihexyl-[2,2’-bithiophene]-5,5’-diyl)bis(ethyne-2,1-diyl)bis(4,1-phenylene)bis(2,6-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)pyridine-3,5-dicarbonitrile) (8). Two equiv of 4 per 1 equiv of 5,5’-diethynyl-3,3’-dihexyl-[2,2’]bithiophene were employed. After evaporation of the solvent the crude product

Synthesis, optical and electrochemical properties of (D–π)₂-type and (D–π)₂Ph-type fluorescent dyes

• Kosuke Takemura,
• Kazuki Ohira,
• Taiki Higashino,
• Keiichi Imato and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2022, 18, 1047–1054, doi:10.3762/bjoc.18.106

• '-bithiophene]-5,5'-diyl)bis(9-butyl-N,N-diphenyl-9H-carbazol-2-amine) (OTT-2): A solution of 1 (87 mg, 0.137 mmol), 1,3-diiodobenzene (14 mg, 0.041 mmol), and Pd(PPh3)4 (2 mg, 0.001 mmol) in toluene (1 mL) was stirred for 29 h at 110 ºC under an argon atmosphere. The reaction mixture was diluted with water

Chemical syntheses and salient features of azulene-containing homo- and copolymers

• Vijayendra S. Shetti

Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139

• case of protonated emeraldine. The Nafion membrane doped with protonated polyaminoazulene 31 displayed good proton conductivity and reduced methanol permeability, making it suitable for methanol fuel cell applications. Azulene-containing copolymers Azulene-thiophene/bithiophene copolymers Lai and co

• -workers [27][28], in 2004, reported the synthesis of conjugated polymers containing azulene and bithiophene units, called poly{1,3-bis[2-(3-alkylthienyl)]azulene} 33–38. The 1,3-bis(3-alkylthienyl)azulene 32, synthesized by the Grignard reaction of 1,3-dibromoazulene (4) with 2-bromo-3-alkylthiophene, was

• . The number-average molecular weights (Mn) of polymers 33–38 were in the range 16,000 to 41,000 Da (determined by GPC in THF) and the degree of polymerization was 40–60. The conjugation between the azulene-bithiophene units along the polymer backbone resulted in the red-shifted absorption bands

Recent advances in the application of isoindigo derivatives in materials chemistry

• Andrei V. Bogdanov and
• Vladimir F. Mironov

Beilstein J. Org. Chem. 2021, 17, 1533–1564, doi:10.3762/bjoc.17.111

• ][32][33]. In the course of further studies, the key influence of the nature of both the substituent at the nitrogen atom of isoindigo and at the bithiophene moiety on the OSC efficiency was confirmed. Thus, the introduction of fluorine atoms to thiophene rings in compound 22b leads to an increase in

Synthesis and characterization of S,N-heterotetracenes

• Astrid Vogt,
• Florian Henne,
• Christoph Wetzel,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2020, 16, 2636–2644, doi:10.3762/bjoc.16.214

• (Scheme 1). Synthesis of S,N-heterotetracene H-SN4 13 by thermolysis of azide precursors. Smaller parent heterotriacene dithienopyrrole (H-DTP) was first synthesized by Zanirato et al. by thermolysis of 3-azido-2,2’-bithiophene as the key step [9]. We therefore tried to build up tetracyclic H-SN4 13 via

• 3-nitro-2,2’-bithiophene with triethyl phosphite under microwave irradiation and surprisingly obtained targeted heterotriacene H-DTP (vide supra) with only 11% yield [45]. This result prompted us to have a closer look on the applicability of the Cadogan reaction/cyclization in order to provide S,N

Formal preparation of regioregular and alternating thiophene–thiophene copolymers bearing different substituents

• Atsunori Mori,
• Keisuke Fujita,
• Chihiro Kubota,
• Toyoko Suzuki,
• Kentaro Okano,
• Takuya Matsumoto,
• Takashi Nishino and
• Masaki Horie

Beilstein J. Org. Chem. 2020, 16, 317–324, doi:10.3762/bjoc.16.31

• Rokkodai, Nada, Kobe 657-8501, Japan Department of Chemical Engineering, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan 10.3762/bjoc.16.31 Abstract Differently substituted thiophene–thiophene-alternating copolymers were formally synthesized employing a halo-bithiophene as

• a monomer. Nickel-catalyzed polymerization of bithiophene with substituents at the 3-position, including alkyl-, fluoroalkyl-, or oligosiloxane-containing groups, afforded the corresponding copolymers in good to excellent yield. The solubility test in organic solvents was performed to reveal that

• substituents. We envisaged that such an alternating copolymer in perfect regularity can be achieved by deprotonative polymerization employing a bithiophene with different substituents at the 3- and 3'-position. We have recently shown that the coupling of 2-chloro-3-substituted thiophene 2 with 2-bromo-3

Mono- and bithiophene-substituted diarylethene photoswitches with emissive open or closed forms

• A. Lennart Schleper,
• Mariano L. Bossi,
• Vladimir N. Belov and
• Stefan W. Hell

Beilstein J. Org. Chem. 2019, 15, 2344–2354, doi:10.3762/bjoc.15.227

• with mono- (Th1) and bithiophene (Th2) units attached to positions 6 and 6′ (Sy = symmetric) or only to position 6 (As = asymmetric). “Oxidized” compounds have highly fluorescent closed forms emitting in the visible region (yellow to red). The dyes with nonoxidized benzothiophenes possess fluorescent

• path, even at “one side” of the molecule (in asymmetric compounds) would enable switching with focusable light of 375 nm and above. To test this hypothesis, we designed a series of DAEs with mono- and bithiophene substituents attached to positions 6 and 6′ of an oxidized or a nonoxidized 2-alkylbenzo[b

• regioisomeric bromides were also formed, but they were separated by column chromatography on the next step. Bithiophene 11 was prepared in 74% yield by using a Suzuki–Miyaura coupling (catalyzed by PEPPSI-IPr) between boronic ester 9 and bromide 10 [13][14]. Boronation of bithiophene 11 was achieved under

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

• Pierre-Olivier Schwartz,
• Sebastian Förtsch,
• Astrid Vogt,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2019, 15, 1379–1393, doi:10.3762/bjoc.15.138

• reinvestigated the synthesis of DTT 1 by using a Cu-catalyzed C–S cross-coupling reaction with potassium sulfide (K2S) as sulfur source [29]. The best results for this C–S ring-closure reaction were achieved by reacting 3,3’-diiodo-2,2’-bithiophene (5) [30] with the system K2S and copper iodide (CuI) as catalyst

• DTT 1 in 91% yield (Scheme 1). Triacene dithieno[3,2-b:2’,3’-d]selenophene (DTS, 2) was successfully prepared as well from diiodinated bithiophene 5 in 51% yield after purification in a C–Se cross-coupling/cyclization reaction with selenourea as selenium source, copper oxide nanoparticles as catalyst

• , and potassium hydroxide as base in DMSO (Scheme 1). This method has been previously used for the synthesis of symmetrical diaryl selenides from aryl halides [28]. Attempts to use the corresponding 3,3’-dibromo-2,2’-bithiophene as starting material for the synthesis of either DTS 2 with the same

Synthesis and optical properties of new 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles

• Anastasia S. Kostyuchenko,
• Tatyana Yu. Zheleznova,
• Anton J. Stasyuk,
• Aleksandra Kurowska,
• Wojciech Domagala,
• Adam Pron and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2017, 13, 313–322, doi:10.3762/bjoc.13.34

• ) molecules, namely 5'-aryl-substituted 2,5-bis(3-decyl-2,2'-bithiophen-5-yl)-1,3,4-oxadiazoles were prepared by palladium-catalyzed coupling from readily available compounds such as ethyl 3-decyl-2,2'-bithiophene-5-carboxylate and aryl halides. The obtained compounds feature increasing bathochromic shifts in

• by quantum chemical DFT/TDDFT calculations carried out for these new molecules. Keywords: bithiophene; donor–acceptor; luminescence; 1,3,4-oxadiazole; palladium-catalyzed coupling; Introduction π-Conjugated donor–acceptor (D-A) compounds are of significant scientific interest because they

• frequently combine solution processability with unique electronic, luminescent and electrochemical properties [1][2][3][4][5]. Molecules in which a central electron-accepting ring separates two bithiophene units are of particular interest [6][7][8][9][10][11][12][13][14][15]. The continuing progress in this

Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• ], where D1 is an electron-rich unit such as bithiophene, A is a benzothiadiazole derivative and D2 can be different electron-rich planar cores such as dithienosilol or silanindacenodithiophene. Utilizing this push–pull molecular approach, efficiencies up to 9.0% have been achieved [13] due to deep highest

• -silolo[3,2-b]thiophene-2,2′-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole, p-SIDT(FBTTh2)2, (Figure 1), we have modified the conjugated backbone to include electron-withdrawing octyl cyanoacetate (CA8) end groups, essentially forming an “A1–D1–A2–D2–A2–D1–A1” molecular

High performance p-type molecular electron donors for OPV applications via alkylthiophene catenation chromophore extension

• Paul B. Geraghty,
• Calvin Lee,
• Jegadesan Subbiah,
• Wallace W. H. Wong,
• James L. Banal,
• Mohammed A. Jameel,
• Trevor A. Smith and
• David J. Jones

Beilstein J. Org. Chem. 2016, 12, 2298–2314, doi:10.3762/bjoc.12.223

• -donor– π-bridge-acceptor (A–π-D–π-A) electron donor molecules. Based on the known benzodithiophene-terthiophene-rhodanine (BTR) material, the BXR series of materials, BMR (X = M, monothiophene), BBR (X = B, bithiophene), known BTR (X = T, terthiophene), BQR (X = Q, quaterthiophene), and BPR (X = P(penta

•  1), where we have varied the chromophore length through the BXR series, where X = monothiophene (M), bithiophene (B), the known terthiophene (T), quaterthiophene (Q), and quinquethiophene (P), respectively and allowing isolation of products on the multigram scale. The simplified synthesis was

• -bromothiophene-2-carboxaldehyde to generate the bithiophene 4, Scheme 3. It has previously been reported that direct coupling of 2-(trimethylsilyl)thiophene with aryl halides proceeds in good yield with protodesilylation being the major side reaction under the reaction conditions, even at short reaction times

Regiocontroled Pd-catalysed C5-arylation of 3-substituted thiophene derivatives using a bromo-substituent as blocking group

• Mariem Brahim,
• Hamed Ben Ammar,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2016, 12, 2197–2203, doi:10.3762/bjoc.12.210

• -arylation of the 2-bromo-3-methylthiophene with itself to produce 5'-bromo-3,4'-dimethyl-2,2'-bithiophene was observed. Then, from the C2-heteroarylated 3-methylthiophenes 21–23, a second direct arylation at position C5 allows to prepare the products 24–26 in 87–91% yields (Scheme 7). The synthesis of 3

Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• of the π-bridges. In this respect, oligothiophenes, including monotiophene [16][20], bithiophene [16], terthiophene [8][14][15][17][18][19][21][22][23][26], quaterthiophene and quinquethiophene [27], and cyclopentadithiophene [28] have been utilized as the π-bridge in constructing conjugated

• ), TBDT = 4,8-bis(5-alkyl-2-thienyl)benzo[1,2-b:4,5-b′]dithiophene) is shown in Scheme 1. The bithiophene building block, 3,4'-dihexyl-5'-iodo-2,2'-bithiophene-5-carbaldehyde (11) was synthesized by an ipso-substitution of 10, which was synthesized by a Suzuki coupling of 9 with 6, with ICl. The

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• oxidation potential of TTF and that of the thiophene backbone of the monomer, the TTF-modified bithiophene compounds 5b–d were used as monomers for electropolymerisation to 6b–d [49]. The appearance of an additional, well-defined oxidation wave in the CV, as the first oxidation wave was split in both anodic

• electropolymerised monomer 5c (2 × 10−2 M) in the presence of a double excess of a non-modified bithiophene monomer 7 [49], the contribution from the PT backbone oxidation in the CV of the final copolymer was clear. However, it was unresolved from the wave of TTF2+ formation during the anodic run (Figure 1). An

• dark purple solid in 95% yield [55]. Polymer 35 is the analogue of the polymer which could have been obtained had the monomer 14a been suitable for electropolymerisation, while Stille coupling of dibromo monomer 14b with 5,5'-bis(trimethylstannyl)-2,2'-bithiophene (36) [78] was used to circumvent

Functionalized branched EDOT-terthiophene copolymer films by electropolymerization and post-polymerization “click”-reactions

• Miriam Goll,
• Adrian Ruff,
• Erna Muks,
• Felix Goerigk,
• Beatrice Omiecienski,
• Ines Ruff,
• Rafael C. González-Cano,
• Juan T. Lopez Navarrete,
• M. Carmen Ruiz Delgado and
• Sabine Ludwigs

Beilstein J. Org. Chem. 2015, 11, 335–347, doi:10.3762/bjoc.11.39

• the electropolymerization can be regarded as a crosslinking step [17][18]. Electropolymerization of monomer mixtures is another powerful tool to modify material properties. Among a variety of monomer mixtures including pyrrole and thiophene [19][20], 2,2’-bithiophene and pyrrole [21][22] and

• modified bithiophene followed by bipyrrole monomers [38]. In some cases the direct polymerization of ionically modified monomers remains problematic: this was for example reported in the case of sulfonic acid modified pyrrole, where film deposition was only possible when a copolymerization with pristine

Palladium-catalyzed 2,5-diheteroarylation of 2,5-dibromothiophene derivatives

• Fatma Belkessam,
• Aidene Mohand,
• Jean-François Soulé,
• Abdelhamid Elias and
• Henri Doucet

Beilstein J. Org. Chem. 2014, 10, 2912–2919, doi:10.3762/bjoc.10.309

• 2-bromothiophene (Scheme 6). The reaction of 1 equiv thiophene with 2 equiv of 2-bromothiophene resulted in a poor yield for 7 due to the formation of a mixture of bithiophene 32, terthiophene 7 and also a quaterthiophene (as was observed by GC–MS analysis of the crude mixture). On the other hand

Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin

• Jun Terao,
• Yohei Konoshima,
• Akitoshi Matono,
• Hiroshi Masai,
• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2014, 10, 2800–2808, doi:10.3762/bjoc.10.297

• synthesized from 1 using sodium naphthalenide [27]. The reaction of the thus-formed monoalcohol with 2-bromo-3-(bromomethyl)thiophene (11) afforded thiophene-linked PM β-CD 12. Pd-catalyzed Stille cross-coupling of 12 with bithiophene 13 bearing a silyl-protected alkynyl group afforded trithiophene-linked PM

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• was synthesised (compound 7). The synthesis of 7 was achieved from the α-brominated derivative of bithiophene carbaldehyde 4. This synthetic route to prepare 7 has been described previously in the literature [47]. Formylation of the bithiophene was carried out using Vilsmeier–Haack conditions by

• ], and 7 [47] were prepared according to the literature. 10,10'-(5',5'''-(2,5-Bis(2-octyldodecyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4-c]pyrrole-1,4-diyl)bis([2,2'-bithiophene]-5',5-diyl))bis(2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-4-ium-5-uide) (9

Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4-thiadiazole and 1,2,4-triazole

• Anastasia S. Kostyuchenko,
• Vyacheslav L.Yurpalov,
• Aleksandra Kurowska,
• Wojciech Domagala,
• Adam Pron and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2014, 10, 1596–1602, doi:10.3762/bjoc.10.165

• synthetic approach towards the preparation of functionalised, soluble, donor–acceptor (DA) alkylbithiophene derivatives of oxadiazole, thiadiazole and triazole is reported. Taking advantage of the Fiesselmann reaction, reactive bithiophene synthons having alkyl or alkoxy substituents at designated positions

• functionalised oligothiophenes, coupled to other heteroaromatic cores. Keywords: bithiophene; donor–acceptor; luminescence; 1,3,4-oxadiazole; 1,3,4-thiadiazole; 4H-1,2,4-triazole; Introduction In the past two decades oligo- and polythiophenes gained a significant research interest due to their wide application

• (aryl) substituted esters of 2,2'-bithiophene-5-carboxylic acids, which is based on a modification of the Fiesselmann reaction [11][23]. Ethyl 3-decyl-2,2'-bithiophene-5-carboxylate (3) was obtained by this method in 80–85% yields at each step [24] (Scheme 1). Ethyl 3-oxo-3-(2-thienyl)propanoate (4

Amyloid-β probes: Review of structure–activity and brain-kinetics relationships

• Todd J. Eckroat,
• Abdelrahman S. Mayhoub and
• Sylvie Garneau-Tsodikova

Beilstein J. Org. Chem. 2013, 9, 1012–1044, doi:10.3762/bjoc.9.116

• clearance and less nonspecific binding in the brains of normal mice, a typical result for brain imaging probes. One of the most promising compounds identified in this study was [125I]59d. The [125I]-labeled benzothiazole bithiophene 60 was synthesized by condensation of 5-bromo-2-aminobenzenethiol and 2,2

• '-bithiophene-5-carbaldehyde followed by installation of the radiolabel. In in vitro binding experiments, 60 displayed high affinity for both Aβ1-40 and Aβ1-42 aggregates with Ki values of 0.25 nM and 0.31 nM, respectively. In addition, it was used to clearly visualize Aβ plaques in AD brain sections and showed

Ring-opening reaction of 2,5-dioctyldithieno[2,3-b:3',2'-d]thiophene in the presence of aryllithium reagents

• Hao Zhong,
• Jianwu Shi,
• Jianxun Kang,
• Shaomin Wang,
• Xinming Liu and
• Hua Wang

Beilstein J. Org. Chem. 2013, 9, 767–774, doi:10.3762/bjoc.9.87

• ring-opening reaction of 2,5-dioctyldithieno[2,3-b:3',2'-d]thiophene with aryllithium in THF at low temperature to generate 2'-arylthio-3,3'-bithiophene-2-carbaldehydes is studied. Nine examples are explored and all the products are characterized by 1H NMR, 13C NMR and HRMS. The relative relationship

• between the structures of aryl groups and the efficiency of ring-opening reactions are discussed. Keywords: aryllithium reagents; 2'-arylthio-3,3'-bithiophene-2-carbaldehyde; dithieno[2,3-b:3',2'-d]thiophene; nucleophilicity; ring-opening reaction; Introduction Due to the promising optical and

• the synthesis of a series of symmetric substituted dithieno[2,3-b:3',2'-d]thiophenes and their ring-opening reactions in the presence of n-BuLi. The 3,3'-bithiophene-2-carbaldehydes were generated after quenching with an electrophile, i.e., dry DMF (Scheme 1) [5]. The uncommon ring opening of fused

Synthesis and characterization of low-molecular-weight π-conjugated polymers covered by persilylated β-cyclodextrin

• Aurica Farcas,
• Ana-Maria Resmerita,
• Andreea Stefanache,
• Mihaela Balan and
• Valeria Harabagiu

Beilstein J. Org. Chem. 2012, 8, 1505–1514, doi:10.3762/bjoc.8.170

• -dioctylfluorene)-alt-5,5'-bithiophene/PS-βCD] (PDOF-BTc) polyrotaxane copolymer, through a Suzuki coupling reaction between the 5,5'-dibromo-2,2'-bithiophene (BT) inclusion complex with persilylated β-cyclodextrin (PS-βCD), and 9,9-dioctylfluorene-2,7-bis(trimethylene borate) (DOF) as the blocking group. The

• bulkier silylated groups, affecting the ability of the diborate groups from the DOF molecule to partially penetrate the PS-βCD cavity. Keywords: alternating fluorene-bithiophene copolymer; cyclodextrins; interlocked molecules; macrocycles; persilylated β-cyclodextrin; polyrotaxanes; Introduction Organic

• wide emission band during operation [8]. Taking into account the relevant photophysical properties of these organic compounds, new synthetic approaches were developed. Copolymerization of fluorene with thiophene, bithiophene or other aromatic comonomers is an alternative method for tuning the optical

Thiophene-based donor–acceptor co-oligomers by copper-catalyzed 1,3-dipolar cycloaddition

• Stefanie Potratz,
• Amaresh Mishra and
• Peter Bäuerle

Beilstein J. Org. Chem. 2012, 8, 683–692, doi:10.3762/bjoc.8.76

• , 51.58; H, 3.11; N, 17.98; S, 27.73; CIMS m/z: (M + H) 234, (M − N2) 206, (M − C4H3N2S) 122. 4-(2,2'-Bithien-5-yl)-1-(thien-2-yl)-1H-1,2,3-triazole (12): 2-Iodothiophene (3, 0.11 mL, 1 mmol), 5-ethynyl-2,2'-bithiophene (190 mg, 1 mmol), sodium azide (130 mg, 2 mmol), copper(I) iodide (19 mg, 0.1 mmol

• C14H9N3S3: C, 53.31; H, 2.88; N, 13.32; S, 30.49; found: C, 53.27; H, 3.00; N, 13.24; S, 30.32; CIMS m/z: (M + H) 316, (M − N2) 288. 1-(2,2'-Bithien-5-yl)-4-(thien-2-yl)-1H-1,2,3-triazole (13): 5-Iodo-2,2'-bithiophene (317 mg, 1 mmol), 2-ethynylthiophene (0.11 mg, 1 mmol), sodium azide (130 mg, 2 mmol

• , 128.05, 131.95, 135.89; CIMS m/z: (M+) 316, (M − N2) 288; HRMS–ESI (m/z): (M + Na) calcd for C14H9N3NaS3, 337.9851; found, 337.9847; (M + H) calcd for C14H10N3S3, 316.0031; found, 316.0026. 1,4-Di(2,2'-bithien-5-yl)-1H-1,2,3-triazole (14): 5-Iodo-2,2'-bithiophene (0.92 g, 1 mmol), 5-ethynyl-2,2

Syntheses and properties of thienyl-substituted dithienophenazines

• Annemarie Meyer,
• Eva Sigmund,
• Friedhelm Luppertz,
• Gregor Schnakenburg,
• Immanuel Gadaczek,
• Thomas Bredow,
• Stefan-S. Jester and
• Sigurd Höger

Beilstein J. Org. Chem. 2010, 6, 1180–1187, doi:10.3762/bjoc.6.135

• scanning tunneling microscopy (STM). Synthesis The synthesis of 4 is shown in Scheme 1. It is obtained in three steps from commercially available starting materials. The synthesis of 3 has previously been reported by benzoin condensation of the corresponding bithiophene derivative [18]. Alternatively, we

• quantitative yield [21][22]. The respective regio isomer 8 was synthesized starting from commercially available 3-bromothiophene 1 and boronic acid 5 in three steps (Scheme 2). By Suzuki–Miyaura coupling we obtained 3,3’-bithiophene in good yields. The red diketone 7 was prepared by two-fold acylation with

• oxalyl chloride [23][24]. Bromination of 7 with NBS failed, however, the reaction with bromine under similar conditions as described for 4 afforded 8 in quantitative yields. Both routes towards the brominated bithiophene-diketones gave high overall yields and can be scaled up easily. Condensation of the

Self-assembly and semiconductivity of an oligothiophene supergelator

• Pampa Pratihar,
• Suhrit Ghosh,
• Vladimir Stepanenko,
• Sameer Patwardhan,
• Ferdinand C. Grozema,
• Laurens D. A. Siebbeles and
• Frank Würthner

Beilstein J. Org. Chem. 2010, 6, 1070–1078, doi:10.3762/bjoc.6.122

• on bisurea derivatives of bithiophene chromophores and demonstrated a significant charge carrier mobility as a result of self-assembly (Σμmin = 5 × 10−3 cm2 V−1 s−1) [18]. However, the building blocks were made only from mono and bithiophene units. Later, Shinkai and co-workers reported the gelation

• -containing building block 6 in 78% yield. 2, 2´-Bithiophene was converted to the corresponding tributyltin derivative 8 by the reported procedure [19] and then coupled with compound 6 in the presence of a Pd-catalyst to give the desired oligothiophene derivative T1 in 82% yield. The new compounds 6 and T1

• mono- and bithiophene bisurea compunds [18]. Therefore, the charge transport properties of T1 in the solid state were investigated by pulse radiolysis time resolved microwave conductivity (PR-TRMC) measurements [27]. PR-TRMC measurements were performed with a solid (powder) sample of T1 using the same