17573-92-1Relevant articles and documents
Facile C-S Bond Cleavage of Aryl Sulfoxides Promoted by Bronsted Acid
Brutiu, Bogdan R.,Klose, Immo,Maulide, Nuno
supporting information, p. 488 - 490 (2021/03/09)
A method for the Bronsted acid promoted desulfination of aryl sulfoxides is presented. In the presence of a thiol, electron-rich sulfoxides undergo C-S bond cleavage to give the corresponding protodesulfinated arenes and disulfides.
Role of Substituents at 3-position of Thienylethynyl Spacer on Electronic Properties in Diruthenium(II) Organometallic Wire-like Complexes
Roy, Sourav Saha,Chowdhury, Sabyasachi Roy,Mishra, Sabyashachi,Patra, Sanjib K.
, p. 3304 - 3313 (2020/09/09)
A series of organometallic complexes [Cl(dppe)2Ru?C≡C-(3-R?C4H2S)-C≡C?Ru(dppe)2Cl] (3-R-C4H2S=3-substituted thienyl moiety; R=?H, ?C2H5, ?C3H7, ?C4H9, ?C6H13, ?OMe, ?CN in 5 a–5 g respectively) have been synthesized by systematic variation of 3-substituents at the thienylethynyl bridging unit. The diruthenum(II) wire-like complexes (5 a–5 g) have been achieved by the reaction of thienylethynyl bridging units, HC≡C-(3-R-C4H2S)-C≡CH (4 a–4 g) with cis-[Ru(dppe)2Cl2]. The wire-like diruthenium(II) complexes undergo two consecutive electrochemical oxidation processes in the potential range of 0.0 - 0.8 V. Interestingly, the wave separation between the two redox waves is greatly influenced by the substituents at the 3-position of the thienylethynyl. Thus, the substitution on 3-position of the thienylethynyl bridging unit plays a pivotal role for tuning the electronic properties. To understand the electronic behavior, density functional theory (DFT) calculations of the selected diruthenium wire-like complexes (5 a–5 e) with different alkyl appendages are performed. The theoretical data demonstrate that incorporation of alkyl groups to the thienylethynyl entity leaves unsymmetrical spin densities, thus affecting the electronic properties. The voltammetric features of the other two Ru(II) alkynyl complexes 5 f and 5 g (with ?OMe and ?CN group respectively) show an apparent dependence on the electronic properties. The electronic properties in the redox conjugate, (5 a+) with Kc of 3.9×106 are further examined by UV-Vis-NIR and FTIR studies, showing optical responses in NIR region along with changes in “?Ru?C≡C?“ vibrational stretching frequency. The origin of the observed electronic transition has been assigned based on time-dependent DFT (TDDFT) calculations.
Correlation of structure and photovoltaic performance of benzo[1,2-b:4,5-b′]dithiophene copolymers alternating with different acceptors
Yu, Jiangsheng,Zhao, Baofeng,Nie, Xuemei,Zhou, Baojin,Li, Yang,Hai, Jiefeng,Zhu, Enwei,Bian, Linyi,Wu, Hongbin,Tang, Weihua
supporting information, p. 2248 - 2255 (2015/03/18)
Four π-conjugated benzo[1,2-b:4,5-b′]dithiophene (BDT) based polymers were synthesized for application in polymer solar cells. These polymers possessed desirable HOMO/LUMO levels for polymer photovoltaic applications. PBDTT-TTz and PBDTT-DTBT displayed strong absorption in the range of 300-650 nm, while PBDTT-DPP and PBDTT-TTDPP showed a further 100 nm extended absorption band. The lowest unoccupied molecular orbital energy levels of polymers were tuned effectively from -3.34 eV to -3.81 eV by fusing with different accepting units. A maximum power conversion efficiency of 2.60% was obtained from photovoltaic cells with a PBDTT-TTz:PC61BM (1:2, w/w) blend film as the active layer, with a short circuit current density of 8.37 mA cm-2, an open circuit voltage of 0.70 V, and a fill factor of 44.3%. This journal is
Triisopropylsilylethynyl substituted benzodithiophene copolymers: Synthesis, properties and photovoltaic characterization
Zhu, Enwei,Luo, Guoping,Liu, Yun,Yu, Jiangsheng,Zhang, Fujun,Che, Guangbo,Wu, Hongbin,Tang, Weihua
supporting information, p. 1595 - 1603 (2015/04/27)
We demonstrated herein the facile synthesis of triisopropylsilylethynyl (TIPS) functionalized benzo[1,2-b:4,5-b′]dithiophene (BDT). Three new TIPSBDT-based donor-acceptor alternating copolymers were further developed by Pd-catalyzed Stille coupling. The effect of accepting unit structure on the optical, electrochemical and energy levels of the polymer was studied. The positive impact of PFN layer, high-boiling solvents processing, polar solvent treatment and solvent annealing on the performance of polymer:PC71BM bulk heterojunction solar cells was revealed. The best devices delivered a power conversion efficiency of 5.46% when blend films processed using o-dichlorobenzene with 3 vol% DIO and treated with the optimization of THF annealing and insertion of PFN layer. The device performance was correlated with the morphology evolution of blend films processed with solvent choice, methanol treatment and THF annealing.
A ligand-free, powerful, and practical method for methoxylation of unactivated aryl bromides by use of the CuCl/HCOOMe/MeONa/MeOH system
Guo, Ying,Ji, Si-Zhe,Chen, Cheng,Liu, Hong-Wei,Zhao, Jian-Hong,Zheng, Yu-Lin,Ji, Ya-Fei
, p. 8651 - 8664 (2015/03/05)
A ligand-free, powerful, and practical method for mono and polymethoxylation of unactivated aryl bromides has been developed; CuCl was used as catalyst, HCOOMe as cocatalyst, and methanolic MeONa as both nucleophile and solvent. This eco-friendly procedure is characterized by operational simplicity, inexpensive substrates (unactivated mono to polybromoarenes), full conversion, and direct recovery of pure MeOH.
Thiophene-based salen-type new ligands, their structural aspects and a dimeric Cu(II) complex
Asatkar, Ashish K.,Panda, Snigdha,Zade, Sanjio S.
, p. 25 - 32 (2015/05/20)
A new series of thiophene-based ligands has been developed. The reactions of 2-formyl-3-(hydroxyl/methoxy)thiophene with ethylenediamine yielded the thiophene-based salen ligands 7/8. Whereas the reaction of 2-formyl-3-methoxythiophene with 1,2-diaminobenzene, under similar conditions, unexpectedly, afforded 1,2-substituted benzimidazole based ligand 9. Formation of benzimidazole derivative, without any catalyst, is proposed to be induced by nucleophilic attack of methoxy group. Structures and supramolecular assemblies of all the ligands were studied by single crystal X-ray crystallography. Existence of the different tautomeric forms of ligand 7 was observed in solid and solution phases. The reaction of ligand 7 with CuCl2 afforded a bimetallic complex (7-Cu)2. The structure of (7-Cu)2 was confirmed by single crystal X-ray crystallography. Complex (7-Cu)2 exists in dimeric form through oxygen-copper bridged out-of-plane bonding with Cu(II) in a distorted square pyramidal geometry. Cyclic voltammogram of (7-Cu)2 displayed reversible Cu(II)/Cu(I) redox couple.
Development of Low Energy Gap and Fully Regioregular Polythienylenevinylene Derivative
David, Tanya M. S.,Zhang, Cheng,Sun, Sam-Shajing
, (2015/07/20)
Low energy gap and fully regioregular conjugated polymers find its wide use in solar energy conversion applications.This paper will first briefly review this type of polymers and also report synthesis and characterization of a specific example new polymer, a low energy gap, fully regioregular, terminal functionalized, and processable conjugated polymer poly-(3-dodecyloxy-2,5-thienylene vinylene) or PDDTV. The polymer exhibited an optical energy gap of 1.46 eV based on the UV-vis-NIR absorption spectrum. The electrochemically measured highest occupied molecular orbital (HOMO) level is -4.79 eV, resulting in the lowest unoccupied molecular orbital (LUMO) level of -3.33 eV based on optical energy gap. The polymer was synthesized via Horner-Emmons condensation and is fairly soluble in common organic solvents such as tetrahydrofuran and chloroform with gentle heating. DSC showed two endothermic peaks at 67°C and 227°C that can be attributed to transitions between crystalline and liquid states.The polymer is thermally stable up to about 300°C. This polymer appears very promising for cost-effective solar cell applications.
Fine tuning of polymer properties by incorporating strongly electron-donating 3-hexyloxythiophene units into random and semi-random copolymers
Xu, Bing,Noh, Sangtaik,Thompson, Barry C.
, p. 5029 - 5039 (2014/11/08)
Two series of copolymers containing varying percentages of strongly electron-donating 3-hexyloxythiophene units (3HOT), namely the random poly(3-hexylthiophene-co-3-hexyloxythiophene)s (P3HT-co-3HOTs) and the semi-random poly(3-hexylthiophene-thiophene-3-hexyloxythiophene- diketopyrrolopyrrole)s (P3HTT-HOT-DPPs), were synthesized via Stille polymerization. The influence of 3HOT content on UV-vis absorption, HOMO energy levels, polymer crystallinity, and polymer:PC61BM solar cell performance, especially the open-circuit voltage (Voc), was investigated. Importantly, introduction of the strong donor 3HOT results in regularly decreased band gaps and broadened absorption compared to the corresponding parent polymers, regioregular poly(3-hexylthiophene) (P3HT) and semi-random poly(3-hexylthiophene-thiophene-diketopyrrolopyrrole) (P3HTT-DPP). The HOMO energies of both random P3HT-co-3HOT and semi-random P3HTT-HOT-DPP copolymers increase significantly with 3HOT incorporation, from -5.2 eV to around -4.95 eV with half of the 3-hexylthiophene units (3HT) being replaced by 3HOT, and the trend is directly reflected in the Voc measured in polymer:PC61BM solar cells. High absorption coefficient and semicrystallinity are retained for all of the copolymers. The semi-random P3HTT-HOT-DPP copolymers with low percentage of 3HOT (up to 15%) show J sc of above 10 mA/cm2, which is comparable to the parent P3HTT-DPP. Importantly, this study demonstrates that significant changes in polymer electronic properties can be induced with only small percentage of comonomers in random and semi-random conjugated polymers.
Mild and general palladium-catalyzed synthesis of methyl aryl ethers enabled by the use of a palladacycle precatalyst
Cheung, Chi Wai,Buchwald, Stephen L.
supporting information, p. 3998 - 4001 (2013/09/02)
A general method for the Pd-catalyzed coupling of methanol with (hetero)aryl halides is described. The reactions proceed under mild conditions with a wide range of aryl and heteroaryl halides to give methyl aryl ethers in high yield.
Synthesis and photovoltaic performance of novel thiophenyl-methylene-9H- fluorene-based low bandgap polymers
Hai, Jiefeng,Zhao, Baofeng,Zhang, Fujun,Sheng, Chuan-Xiang,Yin, Liangming,Li, Yang,Zhu, Enwei,Bian, Linyi,Wu, Hongbin,Tang, Weihua
, p. 4930 - 4939 (2013/09/02)
Three novel donor-acceptor polymers have been synthesized with Suzuki cross-coupling between thiophenyl-methylene-9H-fluorene donating unit with thiazolo[5,4-d]thiazole (PFTTTz), benzothiadiazole (PFTODTBT) or [1,2,3]triazolo[4,5-g]quinoxaline (PFTDTBTzQ)
