479719-88-5Relevant articles and documents
Thieno[3,2-b]indole (TI) bridged A-π?D-π?A small molecules: Synthesis, characterizations and organic solar cell applications
Zhou, Xingbao,Lu, Jurong,Huang, Hongyan,Yun, Yikai,Li, Zhaoning,You, Fei,Zhao, Baomin,Qin, Tianshi,Gao, Deqing,Huang, Wei
, p. 16 - 24 (2019)
Two novel A-π-D-π-A small molecules, BDT-TITRh and BDT-TI2TRh, containing alkylthienyl-substituted benzo[1,2-b:4,5-b']dithiophene (BDT) as a core building block, together with 2-(thiophen-2-yl)-N-alkyl-thieno [3,2-b]indole (TIT) or 2,6-di(thiophen-2-yl)-N-alkyl-thieno [3,2-b]indole (TI2T) as π-bridge unit, and 3-ethylrodanine as the electron-withdrawing unit were synthesized, characterized, and employed as the donor materials for BHJ SMOSCs. The impacts of TI π-bridge on the absorption spectra, energy levels, hole mobility, film morphology, and the photovoltaic performance were investigated. The two small molecules both exhibited a high extinction coefficients (～105 M?1 cm?1) and hole mobility (～10?5 cm?2 V?1 s?1) due to the introduction of the extensively conjugated TI as π-bridge unit. A promising PCE of 4.19% with a Jsc of 13.23 mA cm?2 was achieved for the device based on BDT-TI2TRh/PC71BM (1:2, w/w) as the active layer. It is worth mentioning that no additive or thermal annealing was exploited for the fabrication of the current BHJ SMOSCs, and this is an advantage for simplifying the device fabrication and improving the repeatability of the photovoltaic performance. Our preliminary results demonstrate that tricyclic TI as the π-bridge unit can be used for building A-π-D-π-A type small molecules, providing the guidance for the molecular design of high hole mobility SM-materials for efficient BHJ SMOSCs in the future.
Manganese-Catalyzed C(sp2)-H Borylation of Furan and Thiophene Derivatives
Britton, Luke,Skrodzki, Maciej,Nichol, Gary S.,Dominey, Andrew P.,Pawlu?, Piotr,Docherty, Jamie H.,Thomas, Stephen P.
, p. 6857 - 6864 (2021/06/28)
Aryl boronic esters are bench-stable, platform building-blocks that can be accessed through metal-catalyzed aryl C(sp2)-H borylation reactions. C(sp2)-H bond functionalization reactions using rare- and precious-metal catalysts are well established, and while examples utilizing Earth-abundant alternatives have emerged, manganese catalysis remains lacking. The manganese-catalyzed C-H borylation of furan and thiophene derivatives is reported alongside an in situ activation method providing facile access to the active manganese hydride species. Mechanistic investigations showed that blue light irradiation directly affected catalysis by action at the metal center, that C(sp2)-H bond borylation occurs through a C-H metallation pathway, and that the reversible coordination of pinacolborane to the catalyst gave a manganese borohydride complex, which was as an off-cycle resting state.
C-H Borylation Catalysis of Heteroaromatics by a Rhenium Boryl Polyhydride
Donnelly, Liam J.,Faber, Teresa,Morrison, Carole A.,Nichol, Gary S.,Thomas, Stephen P.,Love, Jason B.
, p. 7394 - 7400 (2021/06/30)
Transition metal complexes bearing metal-boron bonds are of particular relevance to catalytic C-H borylation reactions, with iridium polyboryl and polyhydrido-boryl complexes the current benchmark catalysts for these transformations. Herein, we demonstrate that polyhydride boryl phosphine rhenium complexes are accessible and catalyze the C-H borylation of heteroaromatic substrates. Reaction of [K(DME)(18-c-6)][ReH4(Bpin)(ν2-HBpin)(κ2-H2Bpin)] 1 with 1,3-bis(diphenylphosphino)propane (dppp) produced [K(18-c-6)][ReH4(ν2-HBpin)(dppp)] 2 through substitution of two equivalents of HBpin, and protonation of 2 formed the neutral complex [ReH6(Bpin)(dppp)] 3. Combined X-ray crystallographic and DFT studies show that 2 is best described as a σ-borane complex, whereas 3 is a boryl complex. Significantly, the boryl complex 3 acted as a catalyst for the C(sp2)-H borylation of a variety of heteroarenes (14 examples including furan, thiophene, pyrrole and indole derivatives) and displayed similar reactivity to the iridium analogues.
Photocytotoxicity of Thiophene- And Bithiophene-Dipicolinato Luminescent Lanthanide Complexes
Rodrigues, Carime V.,Johnson, Katherine R.,Lombardi, Vincent C.,Rodrigues, Marcelo O.,Sobrinho, Josiane A.,De Bettencourt-Dias, Ana
, p. 7724 - 7734 (2021/06/21)
New thiophene-dipicolinato-based compounds, K2nTdpa (n = 1, 2), were isolated. Their anions are sensitizers of lanthanide ion (LnIII) luminescence and singlet oxygen generation (1O2). Emission in the visible and near-infrared regions was observed for the LnIII complexes with efficiencies (φLn) φEu = 33% and φYb = 0.31% for 1Tdpa2- and φYb = 0.07% for 2Tdpa2-. The latter does not sensitize EuIII emission. Fluorescence imaging of HeLa live cells incubated with K3[Eu(1Tdpa)3] indicates that the complex permeates the cell membrane and localizes in the mitochondria. All complexes generate 1O2 in solution with efficiencies (φO12) as high as 13 and 23% for the GdIII complexes of 1Tdpa2- and 2Tdpa2-, respectively. [Ln(nTdpa)3]3- (n = 1, 2) are phototoxic to HeLa cells when irradiated with UV light with IC50 values as low as 4.2 μM for [Gd(2Tdpa)3]3- and 91.8 μM for [Eu(1Tdpa)3]3-. Flow cytometric analyses indicate both apoptotic and necrotic cell death pathways.
Photocytotoxicity of Oligothienyl-Functionalized Chelates That Sensitize LnIII Luminescence and Generate 1O2
Johnson, Katherine R.,Lombardi, Vincent C.,de Bettencourt-Dias, Ana
supporting information, p. 12060 - 12066 (2020/08/21)
Three new compounds containing a heptadentate lanthanide (LnIII) ion chelator functionalized with oligothiophenes, nThept(COOH)4 (n=1, 2, or 3), were isolated. Their LnIII complexes not only display the characteristic metal-centered emission in the visible or near-infrared (NIR) but also generate singlet oxygen (1O2). Luminescence efficiencies (?Ln) for [Eu1Thept(COO)4]? and [Eu2Thept(COO)4]? are ?Eu=3 percent and 0.5 percent in TRIS buffer and 33 percent and 3 percent in 95 percent ethanol, respectively. 3Thept(COO)44? does not sensitize EuIII emission due to its low-lying triplet state. Near infra-red (NIR) luminescence is observed for all NIR-emitting LnIII and ligands with efficiencies of ?Yb=0.002 percent, 0.005 percent and 0.04 percent for [YbnThept(COO)4]? (n=1, 2, or 3), and ?Nd=0.0007 percent, 0.002 percent and 0.02 percent for [NdnThept(COO)4]? (n=1, 2, or 3) in TRIS buffer. In 95 percent ethanol, quantum yields of NIR luminescence increase and are ?Yb=0.5 percent, 0.31 percent and 0.05 percent for [YbnThept(COO)4]? (n=1, 2, or 3), and ?Nd=0.40 percent, 0.45 percent and 0.12 percent for [NdnThept(COO)4]? (n=1, 2, or 3). All complexes are capable of generating 1O2 in 95 percent ethanol with ?1Ο2 efficiencies which range from 2 percent to 29 percent. These complexes are toxic to HeLa cells when irradiated with UV light (λexc=365 nm) for two minutes. IC50 values for the LnIII complexes are in the range 15.2–16.2 μm; the most potent compound is [Nd2Thept(COO)4]?. The cell death mechanisms are further explored using an Annexin V—propidium iodide assay which suggests that cell death occurs through both apoptosis and necrosis.
Dual selectivity: Electrophile and nucleophile selective cross-coupling reactions on a single aromatic substrate
Heinrich, Annika C. J.,Thiedemann, Birk,Gates, Paul J.,Staubitz, Anne
supporting information, p. 4666 - 4669 (2013/10/08)
The development of a high yielding, both nucleophile and electrophile selective cross-coupling reaction with aromatic rings is presented. The reaction is general with respect to functional groups. Furthermore, the products still contain a boronic ester and a bromide. These two functional groups allow them to be easy-to-prepare, highly complex starting materials for further reactions, avoiding protecting group transformations.
Mechanistic studies into amine-mediated electrophilic arene borylation and its application in MIDA boronate synthesis
Bagutski, Viktor,Del Grosso, Alessandro,Carrillo, Josue Ayuso,Cade, Ian A.,Helm, Matthew D.,Lawson, James R.,Singleton, Paul J.,Solomon, Sophia A.,Marcelli, Tommaso,Ingleson, Michael J.
, p. 474 - 487 (2013/02/25)
Direct electrophilic borylation using Y2BCl (Y2 = Cl2 or o-catecholato) with equimolar AlCl3 and a tertiary amine has been applied to a wide range of arenes and heteroarenes. In situ functionalization of the ArBCl2 products is possible with TMS 2MIDA, to afford bench-stable and easily isolable MIDA-boronates in moderate to good yields. According to a combined experimental and computational study, the borylation of activated arenes at 20 C proceeds through an S EAr mechanism with borenium cations, [Y2B(amine)] +, the key electrophiles. For catecholato-borocations, two amine dependent reaction pathways were identified: (i) With [CatB(NEt 3)]+, an additional base is necessary to accomplish rapid borylation by deprotonation of the borylated arenium cation (σ complex), which otherwise would rather decompose to the starting materials than liberate the free amine to effect deprotonation. Apart from amines, the additional base may also be the arene itself when it is sufficiently basic (e.g., N-Me-indole). (ii) When the amine component of the borocation is less nucleophilic (e.g., 2,6-lutidine), no additional base is required due to more facile amine dissociation from the boron center in the borylated arenium cation intermediate. Borenium cations do not borylate poorly activated arenes (e.g., toluene) even at high temperatures; instead, the key electrophile in this case involves the product from interaction of AlCl3 with Y2BCl. When an extremely bulky amine is used, borylation again does not proceed via a borenium cation; instead, a number of mechanisms are feasible including via a boron electrophile generated by coordination of AlCl3 to Y2BCl, or by initial (heteroarene)AlCl3 adduct formation followed by deprotonation and transmetalation.
Synthesis and transistor properties of asymmetric oligothiophenes: Relationship between molecular structure and device performance
An, Tae Kyu,Jang, Sang Hun,Kim, Seul-Ong,Jang, Jaeyoung,Hwang, Jihun,Cha, Hyojung,Noh, Young Ri,Yoon, Soon Byung,Yoon, Yong Jin,Kim, Lae Ho,Chung, Dae Sung,Kwon, Soon-Ki,Kim, Yun-Hi,Lee, Sang-Gyeong,Park, Chan Eon
, p. 14052 - 14060 (2013/11/06)
A series of three thiophene-naphthalene-based asymmetric oligomers-5-decyl-2, 2′:5′,2″:5″,2′″- quaterthio-phene (DtT), 5-decyl-5″-(naphthalen-2-yl)-2, 2′:5′,2″-terthiophene (D3TN), and 5-(4-decylphenyl)-5′- (naphthalen-2-yl)-2, 2′-bithiophene (DP2TN)-was synthesized by Suzuki cross-coupling reactions. The long alkyl side chains improved both the solubility of the oligomers in solvents and their tendency to self-assemble. UV/Vis absorption measurements suggested that DtT, D3TN, and DP2TN form H-type aggregates with a face-to-face packing structure. In addition, the three oligomers were found to adopt vertically aligned crystalline structures in films deposited on substrates, as revealed by grazing-incidence wide-angle X-ray scattering. These oligomers were used as the active layers of p-type organic field-effect transistors, and the resulting devices showed field-effect mobilities of 3.3×10-3 cm2V-1s -1 for DtT, 1.6 × 10-2cm2V -1s-1 for D3TN, and 3.7 × 10-2cm 2V-1s-1 for DP2TN. The differences in transistor performances were attributed to the degree of π overlap and the morphological differences determined by the molecular structures.
Molecular aggregation-performance relationship in the design of novel cyclohexylethynyl end-capped quaterthiophenes for solution-processed organic transistors
An, Tae Kyu,Hahn, Seung-Hoon,Nam, Sooji,Cha, Hyojung,Rho, Yecheol,Chung, Dae Sung,Ree, Moonhor,Kang, Moon Seong,Kwon, Soon-Ki,Kim, Yun-Hi,Park, Chan Eon
, p. 756 - 762 (2013/03/13)
The synthesis and characterization of cyclohexylethenyl end-capped quaterthiophenes is reported. Additionally, an investigation of the performance of organic field-effect transistors based on these quaterthiophenes in view of the relationship between the solid-state (or aggregate) order and the electronic performance is described. UV-vis absorption measurements revealed that the quaterthiophene with an asymmetrically substituted cyclohexylethynyl end-group induced the formation of H-type aggregates, whereas the quaterthiophene with a symmetrically substituted cyclohexylethynyl end-groups favored the formation of J-type aggregates. Two-dimensional grazing-incidence wide-angle X-ray scattering studies were performed to support the molecular structure-dependent packing of films of the new quaterthiophenes. Solution-processed quaterthiophenes were tested as the active layers of p-type organic field-effect transistors with a bottom gate/top contact geometry. The field-effect mobility of devices that incorporated asymmetric quaterthiophene molecules was quite high, exceeding 0.02 cm2/V s, due to H-aggregation and good in-plane ordering. In contrast, the field-effect mobility of devices that incorporated symmetrical quaterthiophenes, was low, above 5 × 10-4 cm2/(V s), due to the formation of J-aggregates and poor in-plane ordering. A comparison of the symmetrical and asymmetrical quaterthiophene derivatives revealed that the molecular aggregation-dependent packing, determined by the cyclohexylethynyl end groups, was responsible for influencing the organic field-effect transistor performance.
PROCESS FOR THE BORYLATION OF ARENES AND HETEROARYLS
-
Page/Page column 47, (2012/03/26)
This invention relates to a novel process for the borylation of arenes and heteroaryls. The present invention also provides novel borenium cations, which act as electrophiles for electrophilic substitution on the arene or heteroaryl ring, as well as to methodology for the preparation of these cations.
