7333-08-6Relevant articles and documents
Inhibition of carboxylesterases by benzil (diphenylethane-1,2-dione) and heterocyclic analogues is dependent upon the aromaticity of the ring and the flexibility of the dione moiety
Hyatt, Janice L.,Stacy, Vanessa,Wadkins, Randy M.,Yoon, Kyoung Jin P.,Wierdl, Monika,Edwards, Carol C.,Zeller, Matthias,Hunter, Allen D.,Danks, Mary K.,Crundwell, Guy,Potter, Philip M.
, p. 5543 - 5550 (2005)
Benzil has been identified as a potent selective inhibitor of carboxylesterases (CEs). Essential components of the molecule required for inhibitory activity include the dione moiety and the benzene rings, and substitution within the rings affords increased selectivity toward CEs from different species. Replacement of the benzene rings with heterocyclic substituents increased the Ki values for the compounds toward three mammalian CEs when using o-nitrophenyl acetate as a substrate. Logarithmic plots of the Ki values versus the empirical resonance energy, the heat of union of formation energy, or the aromatic stabilization energy determined from molecular orbital calculations for the ring structures yielded linear relationships that allowed prediction of the efficacy of the diones toward CE inhibition. Using these data, we predicted that 2,2′-naphthil would be an excellent inhibitor of mammalian CEs. This was demonstrated to be correct with a Ki value of 1 nM being observed for a rabbit liver CE. In addition, molecular simulations of the movement of the ring structures around the dione dihedral indicated that the ability of the compounds to inhibit CEs was due, in part, to rotational constraints enforced by the dione moiety. Overall, these studies identify subdomains within the aromatic ethane-1,2-diones, that are responsible for CE inhibition.
Dinuclear rhenium complexes as redox-active pendants in a novel electrodeposited polycyclopentadithiophene material
Procopio, Elsa Quartapelle,Bonometti, Valentina,Panigati, Monica,Mercandelli, Pierluigi,Mussini, Patrizia R.,Benincori, Tiziana,D'Alfonso, Giuseppe,Sannicol, Francesco
, p. 11242 - 11251 (2014)
The novel [Re2(μ-H)(μ-OOC-CPDT)(CO)6(μ-3-Me-pydz)] complex (1; OOC-CPDT = 4H-cyclopenta[2,1-b:3,4-b′]dithiophene-4-carboxylate, 3-Me-pydz = 3-methylpyridazine) has been prepared and characterized by single-crystal X-ray diffraction, density functional theory (DFT), and time-dependent DFT computations, UV-vis absorption and emission spectroscopy, and cyclic voltammetry (CV). The measured properties indicate the lack of electronic communication in the ground state between the CPDT and the rhenium diazine moieties. Oxidative electropolymerization of 1, achieved by repeated potential cycling (-0.4 to +1.0 V vs Fc+/Fc, in acetonitrile) with different supporting electrolytes, on different electrodes, afforded an electroactive and stable metallopolymer (poly-1). In situ measurements of the mass of the growing film (on a gold electrode, with an electrochemical quartz microbalance) confirmed the regularity of the polymerization process. The polymer exhibits two reversible oxidation peaks of the thiophene chain and a broad irreversible reduction peak (-1.4 V, quite close to that observed for the reduction of monomer 1), associated with a remarkably delayed sharp return peak, of comparable associated charge, appearing in close proximity (+0.3 V) to the first oxidation peak of the neutral polythiophene chain. This charge-trapping effect can be observed upon repeated cycles of p and n doping, and the negative charge is maintained even if the charged electrode is removed from the solution for many hours. Electrochemical impedance spectroscopy showed that the main CV oxidation peak corresponds to facile charge transfer, combined with very fast diffusion of both electrons and ions within the polymer. In summary, poly-1 provides a new example of a metallopolymer, in which the conductive properties of the π-conjugated system are added to the redox behavior of the pendant-isolated complexes. (Figure Presented).
A porous organic polymer supported Pd/Cu bimetallic catalyst for heterogeneous oxidation of alkynes to 1,2-diketones
Chen, Jianbin,Huang, Zhongye,Jia, Xiaofei,Song, Jiaxin,Xie, Congxia,Yang, Zhengyi,Zhang, Kai,Zhao, Jinyu,Zong, Lingbo
, p. 722 - 727 (2022/02/17)
A porous organic polymer (POP-POPh3) was readily prepared by oxidation of POP-PPh3 with H2O2. After coordination with PdCl2 and a co-catalyst of a CuBr2 precursor, a Pd/Cu bimetal-loaded porous organic polymer (Pd/Cu@POP-POPh3) was afforded. The NMR and XPS characterizations indicated that both Pd(ii) and Cu(ii) could coordinate with the PO bonds in the polymer. Furthermore, the catalyst has high surface areas, hierarchical porosity and good thermostability. The Pd/Cu@POP-POPh3 catalyst was successfully used in heterogeneous oxidation of alkynes with O2 as the oxidant to afford corresponding 1,2-diketones in high to excellent yields (76-99%). A series of alkynes with various functional groups performed well in the process. Remarkably, the heterogeneous catalyst can be reused for five cycles without significant loss of catalytic activity in oxidation of diphenylacetylene. This journal is
Dodecacyclic-Fused Electron Acceptors with Multiple Electron-Deficient Units for Efficient Organic Solar Cells
Ma, Shanshan,Feng, Hexiang,Liu, Xiang,Hu, Zhicheng,Yang, Xiye,Liang, Yuanying,Zhang, Jie,Huang, Fei,Cao, Yong
, p. 3544 - 3552 (2021/05/13)
Fused aromatic cores in non-fullerene electron acceptors (NFEAs) play a significant role in determining their optoelectronic properties and photovoltaic performance. In this work, a dodecacyclic-fused core with three electron-deficient units is synthesized through a double intramolecular Cadogan reduction cyclization. Terminal groups with different halogen substitution (F or Cl) are grafted onto the dodecacyclic-fused core to afford MS-4F and MS-4Cl, both of which showed strong and broad absorption, narrow bandgaps around 1.40 eV, and variable molecular packing model in pristine and blend films. Photovoltaic performance of solar cells containing MS-4F and MS-4Cl as NFEAs were investigated with resultant power conversion efficiencies (PCEs) of 11.75 % and 11.79 %, respectively. The mechanism study indicates that both of PBDB-T : MS-4F- and PBDB-T : MS-4Cl-based devices displayed high hole and electron mobility values, efficient charge transfer, and low charge recombination etc. These results indicate that designing multiple-fused aromatic cores with multiple electron-deficient units is a promising strategy to obtain high-performance NFEAs.
A Facile Synthesized Polymer Featuring B-N Covalent Bond and Small Singlet-Triplet Gap for High-Performance Organic Solar Cells
Pang, Shuting,Wang, Zhiqiang,Yuan, Xiyue,Pan, Langheng,Deng, Wanyuan,Tang, Haoran,Wu, Hongbin,Chen, Shanshan,Duan, Chunhui,Huang, Fei,Cao, Yong
supporting information, p. 8813 - 8817 (2021/03/16)
High-efficiency organic solar cells (OSCs) largely rely on polymer donors. Herein, we report a new building block BNT and a relevant polymer PBNT-BDD featuring B-N covalent bond for application in OSCs. The BNT unit is synthesized in only 3 steps, leading to the facile synthesis of PBNT-BDD. When blended with a nonfullerene acceptor Y6-BO, PBNT-BDD afforded a power conversion efficiency (PCE) of 16.1 % in an OSC, comparable to the benzo[1,2-b:4,5-b′]dithiophene (BDT)-based counterpart. The nonradiative recombination energy loss of 0.19 eV was afforded by PBNT-BDD. PBNT-BDD also exhibited weak crystallinity and appropriate miscibility with Y6-BO, benefitting of morphological stability. The singlet–triplet gap (ΔEST) of PBNT-BDD is as low as 0.15 eV, which is much lower than those of common organic semiconductors (≥0.6 eV). As a result, the triplet state of PBNT-BDD is higher than the charge transfer (CT) state, which would suppress the recombination via triplet state effectively.
Mechanophotonics: Flexible Single-Crystal Organic Waveguides and Circuits
Agrawal, Abhijeet R.,Annadhasan, Mari,Bhunia, Surojit,Chandrasekar, Rajadurai,Pradeep, Vuppu Vinay,Reddy, C. Malla,Zade, Sanjio S.
supporting information, p. 13852 - 13858 (2020/06/17)
We present the one-dimensional optical-waveguiding crystal dithieno[3,2-a:2′,3′-c]phenazine with a high aspect ratio, high mechanical flexibility, and selective self-absorbance of the blue part of its fluorescence (FL). While macrocrystals exhibit elasticity, microcrystals deposited at a glass surface behave more like plastic crystals due to significant surface adherence, making them suitable for constructing photonic circuits via micromechanical operation with an atomic-force-microscopy cantilever tip. The flexible crystalline waveguides display optical-path-dependent FL signals at the output termini in both straight and bent configurations, making them appropriate for wavelength-division multiplexing technologies. A reconfigurable 2×2-directional coupler fabricated via micromanipulation by combining two arc-shaped crystals splits the optical signal via evanescent coupling and delivers the signals at two output terminals with different splitting ratios. The presented mechanical micromanipulation technique could also be effectively extended to other flexible crystals.
Dithienobenzimidazole-containing conjugated donor–acceptor polymers: Synthesis and characterization
Harris, Jared D.,Stihl, Markus,Schmidt, Hans-Werner,Carter, Kenneth R.
, p. 60 - 69 (2019/01/03)
The synthesis of two new conjugated polymers based on the relatively under-exploited monomer, 5,8-dibromo-2-[5-(2-hexyldecyl)-2-thienyl]-1H-dithieno[3,2-e:2′,3′-g]benzimidazole (dithienobenzimidazole, DTBI), and either 4,7-bis[4-hexyl-5-(trimethylstannyl)-2-thienyl]-2,1,3-benzothiadiazole (BTD) or 2,6-bis(trimethylstannyl)-4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene (BDT) is described. The polymers were synthesized via Stille polycondensation and characterized by traditional methods (1H NMR, gel-permeation chromatography, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, thermal gravimetric analysis, differential scanning calorimetry, ultraviolet–visible spectroscopy, photoluminescence, and cyclic voltammetry). Prior to their synthesis, trimer structures were modeled by DFT calculations facilitating a further understanding of the systems' electronic and geometric structure. Polymers were titrated with acid and base to take advantage of their amphiprotic imidazole moiety and their optical response monitored with ultraviolet–visible spectroscopy. Finally, pristine polymer thin-films were treated with acid and base to evaluate (de)protonation's effect on system electronics, but thin-film degradation was encountered.
Searching for Models Exhibiting High Circularly Polarized Luminescence: Electroactive Inherently Chiral Oligothiophenes
Benincori, Tiziana,Appoloni, Giulio,Mussini, Patricia Romana,Arnaboldi, Serena,Cirilli, Roberto,Quartapelle Procopio, Elsa,Panigati, Monica,Abbate, Sergio,Mazzeo, Giuseppe,Longhi, Giovanna
, p. 11082 - 11093 (2018/08/01)
Two new inherently chiral oligothiophenes characterized by the atropisomeric 3,3′-bithianaphtene scaffold functionalized with fused ring bithiophene derivatives, namely 4H-cyclopenta[2,1-b3:4b′]dithiophene (CPDT) and dithieno[3,3-b:2′,3′-d]pyrrole (DTP), were synthesized. The racemates were fully characterized and resolved into antipodes by enantioselective HPLC. The enantiomers were analyzed through different chiroptical techniques: electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) were employed to attribute the absolute configuration (AC). Comparison of experimental and calculated VCD spectra confirmed the DFT calculated conformational characteristics. The compound functionalized with two CPDT units was oxidized with FeCl3, and ECD and CPL of the resulting material were measured. Circularly polarized luminescence (CPL) was measured to verify if inherently chiral oligothiophenes could be promising systems for chiral photonics applications.
CO2-assisted synthesis of non-symmetric α-diketones directly from aldehydes: Via C-C bond formation
Hirapara, Pradipbhai,Riemer, Daniel,Hazra, Nabanita,Gajera, Jignesh,Finger, Markus,Das, Shoubhik
supporting information, p. 5356 - 5360 (2017/11/22)
CO2-assisted various symmetric and non-symmetric α-diketones have been synthesized directly from the corresponding aldehydes using transition metal-free catalysts. This method can even be applied to synthesize pharmaceuticals directly from aldehydes. The crucial role of CO2 has been investigated in detail and the mechanism is proposed on the basis of experiments and DFT calculations.
Dithienobenzochalcogenodiazole-based electron donor-acceptor polymers for organic electronics
Efrem, Amsalu,Lei, Yanlian,Wu, Bo,Wang, Mingfeng,Ng, Siu Choon,Ong, Beng S.
, p. 90 - 99 (2016/03/08)
Appositely functionalized dithienobenzo-thiadiazole and dithienobenzo-oxadiazole-monomers were prepared and used in the synthesis of conjugated electron donor-acceptor (D-A) polymers. Detailed systematic investigations were carried out to study the effects of chalcogen atoms and three donor units on the optical and electrochemical properties as well as photovoltaic and field-effect transistor performance of the D-A polymers. All polymers displayed good thermal properties. Polymers containing benzooxadiazole moiety showed deeper LUMO levels as compared to their benzothiadiazole-containing analogues, whereas those derived from weak donor unit exhibited deeper HOMO levels than those with stronger donors. Photovoltaic power conversion efficiency of over 2% and hole field-effect mobility of 2.6 × 10-2 cm2V-1s-1 and on/off ratio of over 105 were obtained. These results demonstrate that dithienobenzo-chalcogenodiazole structures are potentially useful electron acceptor building blocks for the construction of D-A polymers for organic electronics applications.
