The crystal structures of three 5‐alkenyl‐2‐arylthieno[3,2‐b]thiophenes, namely 3,6‐dibromo‐5‐(4‐tert‐butylstyryl)‐2‐(naphthalen‐1‐yl)thieno[3,2‐b]thiophene, C28H22Br2S2, (I), 3,6‐dibromo‐5‐(4‐methylstyryl)‐2‐(naphthalen‐1‐yl)thieno[3,2‐b]thiophene, C25H16Br2S2, (II), and 3,6‐dibromo‐2‐(4‐tert‐butylphenyl)‐5‐(4‐methylstyryl)thieno[3,2‐b]thiophene, C25H22Br2S2, (III), have been determined in order to evaluate the geometry of the molecules. The π‐conjugated system containing the thieno[3,2‐b]thiophene skeleton, the ethylene bridge and the phenyl rings is almost planar. The aromatic ring directly attached to the thieno[3,2‐b]thiophene moiety is not coplanar with the thieno[3,2‐b]thiophene moiety itself due to steric hindrance of the bromo substituent. The crystal packings are characterized by π–π stacking [only for (II)] and C—Br...π interactions. The long axes of the molecules in (I) are oriented in two directions; for the two other structures the long axis is oriented in one direction only. 相似文献
The authors study adjustable bandgap properties of the novel triple chalcogenophene‐based polymer poly‐(3‐hexyl‐2(3‐(4‐hexylthiophene‐2‐yl)‐4,5‐butylselenophene‐1‐yl)‐5‐(4,5‐butyltellurophene‐1‐yl)thiophene) through a combination of morphological, spectroscopic, and computational techniques. The bandgap can be tuned after polymerization by means of mild temperature annealing, which will allow for a partnership with a broader range of donor/acceptor molecules, a property that makes it potentially suitable for organic photovoltaic implementation. The bandgap is modified by selection of the annealing temperatures, and the process is arguably related to the aggregation of tellurophene units, as similar effects are observed in polytellurophenes. Moreover, adequate chemistry engineering ensures easy solution processability and attainment of homogeneous films, which is also essential for applications.
An eco‐friendly method has been developed for the synthesis of 2‐amino‐4‐(9H‐carbazole‐3‐yl)thiophene‐3‐carbonitriles from preliminary carbazole ( 1 ) through an intermediate of 2‐(1‐(9H‐carbazole‐3‐yl)ethylidene)malononitriles using the Knoevenagel condensation followed by the Gewald reaction. On the other hand, the target compounds could also be prepared in a one‐pot three‐component manner by treating equimolar quantities of 1‐(9H‐carbazole‐3‐yl)ethanone ( 3 ), malononitrile, and elemental sulfur. The merits of this preparation are mild reaction conditions. The Gewald reaction is executed with inorganic base NaHCO3 (H2O) in tetrahydrofuran, easy work‐up procedure with good yields. 相似文献
The crystal structures of the title compounds, 2α,4α‐dibenzyl‐3α‐tropanol (2α,4α‐dibenzyl‐8‐methyl‐8‐azabicyclo[3.2.1]octan‐3α‐ol), C22H27NO, (I), and 2α,4α‐dibenzyl‐3β‐tropanol (2α,4α‐dibenzyl‐8‐methyl‐8‐azabicyclo[3.2.1]octan‐3β‐ol), C22H27NO, (II), show that both compounds have a piperidine ring in a chair conformation and a pyrrolidine ring in an envelope conformation. Isomer (I) is asymmetric, the benzyl groups having different orientations, whereas isomer (II) is mirror symmetric, and the N and O atoms, the C atom attached to the hydroxy group, and the methyl C atom attached to the N atom lie on the mirror plane. In the crystal structures of both (I) and (II), the molecules are linked together by intermolecular O—H⋯N hydrogen bonds to form chains that run parallel to the a direction in (I) and parallel to b in (II). 相似文献
An efficient multi‐component synthesis of highly functionalized 2,2′‐bifurans and 2‐(thiophen‐2‐yl)furans is described. A mixture of furan‐ or thiophene‐2‐carbonyl chloride, an isocyanide, and a dialkyl acetylenedicarboxylate undergoes a smooth addition reaction in dry CH2Cl2 at ambient temperature to produce 2‐amino‐5‐(4‐chlorofuran‐2‐yl)furan‐3,4‐dicarboxylates and 2‐amino‐5‐(4‐chlorothiophen‐2‐yl)furan‐3,4‐dicarboxylates. A single‐crystal X‐ray‐analysis of a derivative conclusively confirms the structure of these 2,2′‐bifurans and 2‐(thiophen‐2‐yl)furans. A novel electrophilic aromatic substitution reaction can justify the formation of the Cl‐substituted furan or thiophene rings. 相似文献
Demonstrated in this work is a simple random ternary copolymerization strategy to synthesize a series of polymer acceptors, PTPBT‐ETx, by polymerizing a small‐molecule acceptor unit modified from Y6 with a thiophene connecting unit and a controlled amount of an 3‐ethylesterthiophene (ET) unit. Compared to PTPBT of only Y6‐like units and thiophene units, PTPBT‐ETx (where x represents the molar ratio of the ET unit) with an incorporated ET unit in the ternary copolymers show up‐shifted LUMO energy levels, increased electron mobilities, and improved blend morphologies in the blend film with the polymer donor PBDB‐T. And the all‐polymer solar cell (all‐PSC) based on PBDB‐T:PTPBT‐ET0.3 achieved a high power conversion efficiency over 12.5 %. In addition, the PTPBT‐ET0.3‐based all‐PSC also exhibits long‐term photostability over 300 hours. 相似文献
α‐Iminopyridine (α‐IP) is an important redox‐noninnocent ligand. The substituents on the imino function of α‐IPs have important impact on the reaction selectivity with diethylzinc. For the α‐IPs with a hydrogen substituent on the imino carbon, reduction occurred for the non‐bulky N‐substituents phenyl and 2‐methylphenyl groups, whereas alkyl addition and coupling reactions can be selectively achieved for the sterically bulky N‐substituents 2,6‐dimethylphenyl or 2,4,6‐trimethylphenyl group. However, for the α‐IPs with a CH3 substituent on the imino carbon, the deprotonation reaction happened regardless of the N‐substituents of 2‐methylphenyl or 2,6‐dimethylphenyl group. All the products were isolated and characterized by single‐crystal X‐ray diffraction. The possible mechanisms of these reactions were also discussed. 相似文献
In a rational chiral molecular design of chalcogenides, optically active thiepin with C2‐symmetric chirality was synthesized from commercially available thiophene. Then enatioselective Chalcogeno‐Baylis‐Hillman reactions of arylaldehydes with methyl vinyl ketone (MVK) and acrylates were investigated in the presence of thiepin‐Lewis acid complex. Finally, up to 64% ee was achieved in the presence of 0.2 equiv. of (S)‐thiepin at 20°C. 相似文献
In this study, we report the synthesis a series of novel 2‐[N‐(1H‐tetrazol‐5‐yl)‐6,14‐endo‐etheno‐6,7,8,14‐tetrahydrothebaine‐7α‐yl]‐5‐phenyl‐1,3,4‐oxadiazole derivatives ( 7a – e ) which have potential opioid antagonist and agonist. The substitution reaction of 6,14‐endo‐ethenotetrahydrothebaine‐7α‐carbohydrazide with corresponding benzoyl chlorides gave diacylhydrazine compounds 4a – e in good yields. The treatment of compounds 4a – e with POCl3 caused the conversion of side‐chain of compounds 5a – e into 1,3,4‐oxadiazole ring at C(7) position; thus, compounds 5a – e were obtained. Subsequently, cyanamides ( 6a – e ) were prepared from compounds 5a – e and then compounds 7a – e were synthesized by the azidation of 6a – e with NaN3. The structures of the compounds were established on the basis of their IR, 1H NMR, 13C APT, 2D‐NMR (COSY, NOESY, HMQC, HMBC) and high‐resolution mass spectral data. 相似文献
The sulfur coordination polymer catena‐poly[zinc(II)‐μ2‐bis[5‐(methylsulfanyl)‐2‐sulfanylidene‐2,3‐dihydro‐1,3,4‐thiadiazol‐3‐ido‐κ2N3:S]], [Zn(C3H3N2S3)2]n or [Zn2MTT4]n, constructed from Zn2+ ions and 5‐methylsulfanyl‐1,3,4‐thiadiazole‐2‐thione (HMTT), was synthesized successfully and structurally characterized. [Zn2MTT4]n crystallizes in the tetragonal space group I (No. 82). Each MTT? ligand (systematic name: 5‐methylsulfanyl‐2‐sulfanylidene‐2,3‐dihydro‐1,3,4‐thiadiazol‐3‐ide) coordinates to two different ZnII ions, one via the thione group and the other via a ring N atom, with one ZnII atom being in a tetrahedral ZnS4 and the other in a tetrahedral ZnN4 coordination environment. These tetrahedral ZnS4 and ZnN4 units are alternately linked by the organic ligands, forming a one‐dimensional chain structure along the c axis. The one‐dimensional chains are further linked via C—H…N and C—H…S hydrogen bonds to form a three‐dimensional network adopting an ABAB‐style arrangement that lies along both the a and b axes. The three‐dimensional Hirshfeld surface analysis and two‐dimensional (2D) fingerprint plots confirm the major interactions as C—H…S hydrogen bonds with a total of 35.1%, while 7.4% are C—H…N hydrogen‐bond interactions. [Zn2MTT4]n possesses high thermal and chemical stability and a linear temperature dependence of the bandgap from room temperature to 270 °C. Further investigation revealed that the bandgap changes sharply in ammonia, but only fluctuates slightly in other solvents, indicating its promising application as a selective sensor. 相似文献
ipso‐Arylative ring‐opening polymerization of 2‐bromo‐8‐aryl‐8H‐indeno[2,1‐b]thiophen‐8‐ol monomers proceeds to Mn up to 9 kg mol?1 with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2‐benzoylphenyl or 2‐(4‐hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=?5.9/?4.0 eV) than poly(3‐hexylthiophene) owing to the electron‐withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10?3 cm2 V?1 s?1) for poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10?6 cm2 V?1 s?1), which suggests such polymers are candidates for n‐type organic semiconductors. Density functional theory calculations suggest that backbone distortion resulting from side‐chain steric interactions could be a key factor influencing charge mobilities. 相似文献
A series of dithienylethene‐containing triarylboranes has been designed, synthesized, and characterized. The electrochemistry, photophysics, and photochromic behavior have also been studied. The photophysical and photochromic properties could be facilely tuned in this system by varying the thiophene spacers (thiophene, thienothiophene, and bithiophene) between the dithienylethene and the dimesitylboron (BMes2) or the position of the BMes2 substitution in the thiophene spacers. The absorption of closed form has been found to be more sensitive towards the structural modification upon incorporation of the BMes2 unit. Moreover, multi‐addressable photochromic reactivity is obtained upon addition of Lewis base (F?), which is due to the formation of boron–Lewis base adduct. The dependence of the photophysical and photochromic properties on the thiophene spacers and the position of the BMes2 substitution has been further supported by computational studies. 相似文献
While exploring the chemistry of tellurium‐containing dichalcogenidoimidodiphosphinate ligands, the first all‐tellurium member of a series of related square‐planar EII(E′)4 complexes (E and E′ are group 16 elements), namely bis(P,P,P′,P′‐tetraphenylditelluridoimidodiphosphinato‐κ2Te,Te′)tellurium(II) (systematic name: 2,2,4,4,8,8,10,10‐octaphenyl‐1λ3,5,6λ4,7λ3,11‐pentatellura‐3,9‐diaza‐2λ5,4λ5,8λ5,10λ5‐tetraphosphaspiro[5.5]undeca‐1,3,7,9‐tetraene), C48H40N2P4Te5, was obtained unexpectedly. The formally TeII centre is situated on a crystallographic inversion centre and is Te,Te′‐chelated to two anionic [(TePPh2)2N]− ligands in an anti conformation. The central TeII(Te)4 unit is approximately square planar [Te—Te—Te = 93.51 (3) and 86.49 (3)°], with Te—Te bond lengths of 2.9806 (6) and 2.9978 (9) Å. 相似文献