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

• Gliwice, Poland Faculty of Chemistry , Warsaw University of Technology, Noakowskiego 3, 00-664 Warszawa, Poland Department of Organic Chemistry, Omsk F.M. Dostoevsky State University, 55a Mira pr., 644077 Omsk, Russian Federation 10.3762/bjoc.13.34 Abstract New photoluminescent donor–acceptor–donor (DAD

• 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

• field calls for elaboration of new synthetic procedures affording tailor-made molecules with tunable physical properties. In this respect, we have recently developed an efficient and flexible approach to the synthesis of π-conjugated donor–acceptor compounds [16][17]. The proposed synthetic pathway

Interactions between photoacidic 3-hydroxynaphtho[1,2-b]quinolizinium and cucurbit[7]uril: Influence on acidity in the ground and excited state

• Jonas Becher,
• Daria V. Berdnikova,
• Darinka Dzubiel,
• Heiko Ihmels and
• Phil M. Pithan

Beilstein J. Org. Chem. 2017, 13, 203–212, doi:10.3762/bjoc.13.23

• , the strongly red-shifted broad absorption and emission bands correspond to the conjugate base 2cB. The red-shifted absorption of 2cB is the result of the formation of the strongly electron-donating oxyanion functionality that leads to a pronounced donor–acceptor interplay with the quinolizinium core

A new class of organogelators based on triphenylmethyl derivatives of primary alcohols: hydrophobic interactions alone can mediate gelation

• Wangkhem P. Singh and
• Rajkumar S. Singh

Beilstein J. Org. Chem. 2017, 13, 138–149, doi:10.3762/bjoc.13.17

• -stacking, donor–acceptor interaction, electrostatic, metal coordination, hydrophobic forces or van der Waals’ interactions [4][5][6]. We know a great deal about the aggregation behaviour of gelator molecules from many studies conducted during the past several years. However, rational design and accurate

• ][21][22]. As mentioned above, developing a new gelator is still largely a trial and error method. The most widely used design strategy involves the inclusion of structural components favouring intermolecular non-covalent interactions (like H-bonding, π-stacking, donor–acceptor interaction, metal

Silyl-protective groups influencing the reactivity and selectivity in glycosylations

• Mikael Bols and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2017, 13, 93–105, doi:10.3762/bjoc.13.12

• than the corresponding benzylated thioglycosides in competition reactions and used the reactivity differences in a one-pot glycosylation reaction between 37, a disarmed donor/acceptor 38 and an acceptor 39, which gave the trisaccharide 40 in a remarkable yield of 88% (Scheme 7). This reaction works so

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

• Pavel Nagorny and
• Zhankui Sun

Beilstein J. Org. Chem. 2016, 12, 2834–2848, doi:10.3762/bjoc.12.283

• attempting to elucidate the nature of halogen complexes have emerged since then; however, the structural features of these interactions were unclear until the work of Mulliken who proposed the formation of donor–acceptor complexes [65][66] and Odd Hassel who conducted crystallographic studies of bromine

Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study

• Nikolay O. Chalkov,
• Vladimir K. Cherkasov,
• Gleb A. Abakumov,
• Andrey G. Starikov and
• Viacheslav A. Kuropatov

Beilstein J. Org. Chem. 2016, 12, 2450–2456, doi:10.3762/bjoc.12.238

• reaction exists in solution as a solvent-separated ion pair with a copper cation. A character of spin-density distribution in a radical anion species leads to the conclusion that the ligand corresponds to type III of the Robin–Day classification. Keywords: acceptor–donor–acceptor triad; bridging ligand

• ; EPR spectroscopy; extended tetrathiafulvalene; protonated semiquinone; Introduction The main idea that led to the creation of the system constructed of two o-quinone terminal moieties bridged with annulated extended tetrathiafulvalene (TTF) insertion, was an attempt to explore acceptor–donor–acceptor

• acceptor–donor–acceptor triad 1. The EPR spectrum of (1·)H in CHCl3, 293 K: a) experimental and b) experimental + D2O. The EPR spectrum of (1·)H3 in CHCl3, 293 K: a) experimental, b) simulated, c) experimental + D2O and d) simulated + D2O. The EPR spectrum of (1·−)H2 THF, 293 K: a) experimental and b

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

• Pierre Boufflet,
• Sebastian Wood,
• Jessica Wade,
• Zhuping Fei,
• Ji-Seon Kim and
• Martin Heeney

Beilstein J. Org. Chem. 2016, 12, 2150–2163, doi:10.3762/bjoc.12.205

• collection. With the thermal stability of all-polymer and polymer-fullerene blend microstructures being particularly problematic [19], block copolymers present a potential solution. Indeed, it has been shown that when block copolymers are used as additives in bulk heterojunction donor–acceptor blend layers

Thiophene-forming one-pot synthesis of three thienyl-bridged oligophenothiazines and their electronic properties

• Dominik Urselmann,
• Konstantin Deilhof,
• Bernhard Mayer and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2016, 12, 2055–2064, doi:10.3762/bjoc.12.194

• [53][54][55] substituted (oligo)phenothiazines. Their pronounced reversible oxidation potentials, their electro- and photochromicity [56], and their luminescence [57][58] have rendered (oligo)phenothiazines interesting candidates as donors in donor–acceptor conjugates with photo-induced electron

• magnitude of the oscillator strengths f, corresponding with significant decadic molar extinction coefficients of the associated bands (Figure 5). In principle these phenothiazine conjugates can be considered as donor–acceptor–donor systems, a topology that can be favorably developed further in molecular

• . This represents in principle a donor–acceptor–donor topology, suitable for further development toward molecular electronics. Studies employing the presented synthetic methodology and the concept of bridging oligophenothiazines with conjugating bridges of variable electronic nature are currently

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• introducing conjugated moieties at the 4′-position [10][11][12]. In this context, the synthesis of tailored terpyridine derivatives with appropriate electron-donor/acceptor moieties may allow for a further improvement of their spectroscopic and electrochemical properties. Owing to its unique fluorescent and

Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells

• Hideaki Komiyama,
• Chihaya Adachi and
• Takuma Yasuda

Beilstein J. Org. Chem. 2016, 12, 1459–1466, doi:10.3762/bjoc.12.142

• acceptor–donor–acceptor electronic structures, an electron-donating TTA unit was coupled with electron-accepting diketopyrrolopyrrole (DPP)-based chromophoric units, which are well-known building blocks used in OSCs [28][29][30][31]. Such molecular structures facilitate intramolecular charge transfer

• to introduce a TTA unit as central electron-donating core into star-shaped and linear π-conjugated oligomers was demonstrated. Multiple electron-accepting DPP arms were attached to the electron-donating TTA core to form star-shaped TTA-DPP4 and linear TTA-DPP2 that have acceptor–donor–acceptor

Molecular weight control in organochromium olefin polymerization catalysis by hemilabile ligand–metal interactions

• Stefan Mark,
• Hubert Wadepohl and
• Markus Enders

Beilstein J. Org. Chem. 2016, 12, 1372–1379, doi:10.3762/bjoc.12.131

• [1] and has been applied for the development of improved transition metal catalysts [2][3][4][5][6][7]. The donor–acceptor interaction of the hemilabile moiety with the metal center should be weak enough to allow the displacement by a substrate, which should itself be transformed during the catalytic

Synergistic chiral iminium and palladium catalysis: Highly regio- and enantioselective [3 + 2] annulation reaction of 2-vinylcyclopropanes with enals

• Haipan Zhu,
• Peile Du,
• Jianjun Li,
• Ziyang Liao,
• Guohua Liu,
• Hao Li and
• Wei Wang

Beilstein J. Org. Chem. 2016, 12, 1340–1347, doi:10.3762/bjoc.12.127

• ; Introduction The power of “donor–acceptor” (D–A) cyclopropanes as versatile 1,3-dipolar components is fuelled by its capacity of serving a complementary approach to a wide array of 5-membered ring structures, which are difficult or impossible to access by classic [3 + 2] cycloaddition reactions [1][2][3][4][5

Reactions of N,3-diarylpropiolamides with arenes under superelectrophilic activation: synthesis of 4,4-diaryl-3,4-dihydroquinolin-2(1H)-ones and their derivatives

• Larisa Yu. Gurskaya,
• Diana S. Belyanskaya,
• Dmitry S. Ryabukhin,
• Denis I. Nilov,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 950–956, doi:10.3762/bjoc.12.93

• rare objects, there is no general method for their synthesis [16][17]. Thus, developing of synthetic method to get these compounds is an actual goal of organic chemistry. Reactions of the series of 3-aryl-N-(aryl)propiolamides 1a–u, bearing various donor–acceptor substituents on aryl rings, with

Enantioselective carbenoid insertion into C(sp³)–H bonds

• J. V. Santiago and
• A. H. L. Machado

Beilstein J. Org. Chem. 2016, 12, 882–902, doi:10.3762/bjoc.12.87

• with the opposite effect. Due to these observations, a carbenoid intermediate can be divided in three different classes based on the electronic nature of the chemical groups attached to its structure: acceptor, donor/acceptor and acceptor/acceptor (Figure 2) [2]. The modification of the substituents on

• the carbenoid intermediate can change its reactivity and hence the selectivity of the carbenoid reaction. The most commonly used diazo compounds rely on the formation of a donor/acceptor carbenoid intermediate type. The EWG increases the electrophilicity and reactivity of the donor/acceptor carbenoid

• )–H when X = Ph or H. The first reason concerns the relative stability of the carbenoids 38-Ph and 38-H. The first one, prepared from the donor/acceptor diazo compound 36-Ph, is 10.9 kcal more stable than the carbenoid 38-H obtained from the acceptor diazo compound 36-H. This observation was

Synthesis and fluorosolvatochromism of 3-arylnaphtho[1,2-b]quinolizinium derivatives

• Phil M. Pithan,
• David Decker,
• Manlio Sutero Sardo,
• Giampietro Viola and
• Heiko Ihmels

Beilstein J. Org. Chem. 2016, 12, 854–862, doi:10.3762/bjoc.12.84

• emission lifetime. Notably, a considerable number of solvatochromic molecules is based on charge-transfer (CT) processes in the excited state resulting from a pronounced donor–acceptor interplay within the fluorophore [8]. Thus, upon excitation of such compounds, a CT – or in charged species a charge shift

• ][12]. Along these lines, we established the annelated quinolizinium ion as a versatile platform for the investigation of cationic chemosensors, especially when the chromophore is incorporated within a donor–acceptor system [13]. In particular, we observed that biaryl-type quinolizinium derivatives

• characteristic of donor–acceptor dyes, namely a cumulative red shift of the emission maximum with increasing solvent polarity, along with a broad, unstructured band structure [1][2]. To assess the effect of the solvent on the emission of compound 6e several different solvents were employed. Unfortunately, many

Scope and mechanism of the highly stereoselective metal-mediated domino aldol reactions of enolates with aldehydes

• M. Emin Cinar,
• Bernward Engelen,
• Martin Panthöfer,
• Hans-Jörg Deiseroth,
• Jens Schlirf and
• Michael Schmittel

Beilstein J. Org. Chem. 2016, 12, 813–824, doi:10.3762/bjoc.12.80

• a decrease of the yield compared with 5a (Scheme 5, Table 7). The best yields were obtained within a series in the case of ketone and aldehyde possessing a donor–acceptor situation. Domino aldol reaction by using a CYTOS™ microreactor Using the CYTOS™ microreactor, a continuous reactor, the

Is conformation a fundamental descriptor in QSAR? A case for halogenated anesthetics

• Maria C. Guimarães,
• Mariene H. Duarte,
• Josué M. Silla and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2016, 12, 760–768, doi:10.3762/bjoc.12.76

• interactions govern the conformational equilibrium in a biological-free environment. Indeed, Lesarri et al. [15] pointed out that anomeric effects owing to donor–acceptor (LP → σ*) interactions are responsible for the conformational preference of isoflurane. Despite the contribution from specific

Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

• Diego M. Andrada,
• Nicole Holzmann,
• Thomas Hamadi and
• Gernot Frenking

Beilstein J. Org. Chem. 2015, 11, 2727–2736, doi:10.3762/bjoc.11.294

• the zeroth-order regular approximation (ZORA) [86]. The nature of the stationary points on the potential energy surface was determined by calculating the vibrational frequencies at BP86/TZ2P+. These calculations were performed with the program package ADF.2013 [87]. The bonding situation of the donor

• –acceptor bonds was investigated by an energy decomposition analysis (EDA) which was developed by Morokuma [88] and by Ziegler and Rauk [89][90]. The bonding analysis focuses on the instantaneous interaction energy ∆Eint of a bond A–B between two fragments A and B in the particular electronic reference

Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• secondary structures from aromatic backbones driven by different noncovalent forces (including hydrogen bonding, donor–acceptor, solvophobicity, and dimerization of conjugated radical cations) and solution-phase supramolecular organic frameworks driven by hydrophobically initiated aromatic stacking in the

• cavity of cucurbit[8]uril (CB[8]) are highlighted. Keywords: donor–acceptor interaction; foldamer; hydrogen bond; radical cation dimerization; supramolecular organic framework; Review Childhood and growing up I was born on July 23rd, 1966 in the small, remote village of Fang-Liu (a combination of two

• the University of South Denmark: donor–acceptor interaction-driven catenanes From October 1994 to December 1995, I performed postdoctoral research with Professor Jan Becher at Odense University (currently University of South Denmark) in Denmark. Through his research career, Professor Becher studied

Synthesis of quinoline-3-carboxylates by a Rh(II)-catalyzed cyclopropanation-ring expansion reaction of indoles with halodiazoacetates

• Magnus Mortén,
• Martin Hennum and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2015, 11, 1944–1949, doi:10.3762/bjoc.11.210

• carbenoids: acceptor-acceptor [9][10][11], mono-acceptor [12] and donor-acceptor [13][14][15][16], and all the carbenoids react preferentially at the electron rich C2–C3 double bond. The catalysts used for the generation of the carbenoids are typically salts of Cu [9][11][13], Rh [10][12][16], Fe [14] and Ru

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

• from those in solution (−4.95/−3.55 eV), which suggested significant donor–acceptor interactions in the solid phase between the DPP and TTF units. OFET device fabrication employing polymer 48 exhibited p-type semiconductor behaviour, with the best performance from devices using the bottom contact top

• dithienyl-thieno-TTF unit and the localised nature of the LUMO led to donor–acceptor interactions in the solid phase, making it impossible for efficient overlap between LUMOs, which would normally be required for an efficient n-type semiconductor. BHJSCs were fabricated from 48 as the electron donor and

• performance is modest compared to that of similar devices fabricated using donor–acceptor block copolymers [88][89][90]. Nevertheless, the value of the PCE (0.31%) is higher than one would expect from a SMOSC fabricated from polymer 48 as a semiconductor, since it has no obvious donor–acceptor phase

Towards inhibitors of glycosyltransferases: A novel approach to the synthesis of 3-acetamido-3-deoxy-D-psicofuranose derivatives

• Maroš Bella,
• Miroslav Koóš and
• Chun-Hung Lin

Beilstein J. Org. Chem. 2015, 11, 1547–1552, doi:10.3762/bjoc.11.170

• complexity of the GnTs catalytic mechanism. The main reasons originating from the complex character of the catalytic mechanism which complicate the search for GnTs inhibitors are a) participation of four components in the transition state (sugar donor, acceptor, nucleotide and metal co-factor), b) weak

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• served as intermediates and model systems in the synthesis of, for example, donor–acceptor systems, chemosensors and materials with molecular electronics applications [44][56]. The N-tosyl protecting group of precursor MPTTFs (4c, 4d, 4f and 4g) must first be removed. This can be achieved in excellent

A hybrid electron donor comprising cyclopentadithiophene and dithiafulvenyl for dye-sensitized solar cells

• Gleb Sorohhov,
• Chenyi Yi,
• Michael Grätzel,
• Silvio Decurtins and
• Shi-Xia Liu

Beilstein J. Org. Chem. 2015, 11, 1052–1059, doi:10.3762/bjoc.11.118

• unit. Keywords: donor–acceptor systems; dye-sensitized solar cells; electrochemistry; intramolecular charge transfer; Knoevenagel reaction; tetrathiafulvalene; Introduction Dye-sensitized solar cells (DSSCs) have been intensively investigated as an alternative to silicon-based solar cells [1][2][3][4

Donor–acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes

• Xiaofeng Lu,
• Jibin Sun,
• Shangxi Zhang,
• Longfei Ma,
• Lei Liu,
• Hui Qi,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 1043–1051, doi:10.3762/bjoc.11.117

• Xiaofeng Lu Jibin Sun Shangxi Zhang Longfei Ma Lei Liu Hui Qi Yongliang Shao Xiangfeng Shao State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Tianshui Southern Road 222, Lanzhou 730000, Gansu Province, P. R. China 10.3762/bjoc.11.117 Abstract A series of donor–acceptor type

• axes. In the type II co-crystals, one fullerene molecule has the donor–acceptor mode similar to that in type I, whereas the other fullerene molecule is substantially surrounded by the aryl groups on Ar-S-TTF molecules and the solvent molecules. Keywords: arylthio-substituted tetrathiafulvalene; co

• -crystal; donor–acceptor system; fullerene; Introduction Tetrathiafulvalene (TTF) [1][2][3] and its derivatives have attracted significant interest for decades. This is because this unique heterocycle system has provided most of the organic conductors possessing diverse electronic ground states [4][5][6