Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• broad absorption band peaking at 494, 491, and 485 nm, respectively, while two absorption bands peaking at 440 and 498 nm were found for 1. Elongation of the π-conjugated bridge leads to a slight hypochromic shift of the absorption band, presumably ascribed to a disorder of the complex structures of the

Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides

• Grzegorz Mlostoń,
• Róża Hamera-Fałdyga,
• Anthony Linden and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2016, 12, 1421–1427, doi:10.3762/bjoc.12.136

• 5b and 5f (with 50% probability ellipsoids; arbitrary numbering of the atoms; only the major disorder conformation of the selenophene ring is shown). Reactions of aromatic thiocarbonyl S-methanides 2a,b with ferrocenyl thioketones 1 (Table 1). Reactions of cycloaliphatic thiocarbonyl S-methanides

Exploring architectures displaying multimeric presentations of a trihydroxypiperidine iminosugar

• Camilla Matassini,
• Stefania Mirabella,
• Andrea Goti,
• Inmaculada Robina,
• Antonio J. Moreno-Vargas and
• Francesca Cardona

Beilstein J. Org. Chem. 2015, 11, 2631–2640, doi:10.3762/bjoc.11.282

• metabolic disorder and Helicobacter pylori infection, as well as in the elucidation of the biological role of α-L-fucosidase in spermiogenesis and sperm maturation [23]. Following our interest in the synthesis of natural alkaloids and their unnatural analogs we recently developed a straightforward synthetic

Inclusion complexes of 2-methoxyestradiol with dimethylated and permethylated β-cyclodextrins: models for cyclodextrin–steroid interaction

• Mino R. Caira,
• Susan A. Bourne,
• Halima Samsodien and
• Vincent J. Smith

Beilstein J. Org. Chem. 2015, 11, 2616–2630, doi:10.3762/bjoc.11.281

• host and guest during complexation [1]. Complex units A and B of TRIMEB·2ME, related by a pseudo-translation of ≈b/2, have nearly identical structural features, namely common TRIMEB host conformations and lack of host disorder, apparent twofold disorder of the 2ME methylene group at C6 (site-occupancy

• O19–H and a host glycosidic O4 atom (O···O 2.894(6) Å). This is evident in the cutaway diagram in Figure 4b. Complex unit C is unique in having neither host nor guest disorder and complex unit D also shows a unique feature, namely disorder in both the C- and D-rings of the 2ME molecule, which is thus

• present as two conformers in the ratio 0.61:0.39. One consequence of this is that there are two distinct positions for the O19–H phenolic group, each conformer forming a hydrogen bond with a different TRIMEB acceptor oxygen atom. Further details of this disorder and its implications are given below

Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

• Sara J. Krivickas,
• Chiho Hashimoto,
• Junya Yoshida,
• Akira Ueda,
• Kazuyuki Takahashi,
• John D. Wallis and
• Hatsumi Mori

Beilstein J. Org. Chem. 2015, 11, 1561–1569, doi:10.3762/bjoc.11.172

• )methyloxazoline)2X, (52X, X = AsF6 [7], PF6 [8]) where disorder within the racemic salt leads to lower conductivity. Recently, Pop et al., have also reported electrical magnetochiral anisotropy in chiral molecular conductors, (R,R)- and (S,S)-[dimethyl-(ethylenedithio)tetrathiafulvalene]2ClO4 (62ClO4) [9][10

Pd(OAc)₂-catalyzed dehydrogenative C–H activation: An expedient synthesis of uracil-annulated β-carbolinones

• Biplab Mondal,
• Somjit Hazra,
• Tarun K. Panda and
• Brindaban Roy

Beilstein J. Org. Chem. 2015, 11, 1360–1366, doi:10.3762/bjoc.11.146

• ]. For example, SL651498 was documented as a potential drug development candidate in a research program designed to discover subtype-selective GABAA receptor agonists for the treatment of muscle spasms and generalized anxiety disorder [13]. β-Carbolinones such as strychnocarpine, the alkaloid from

The chemical behavior of terminally tert-butylated polyolefins

• Dagmar Klein,
• Henning Hopf,
• Peter G. Jones,
• Ina Dix and
• Ralf Hänel

Beilstein J. Org. Chem. 2015, 11, 1246–1258, doi:10.3762/bjoc.11.139

• and angles were unrealistic. Possible sources of error would include disorder, unidentified weak reflections corresponding to a larger cell (the data were recorded on a serial diffractometer), or an incorrect space group. Refinements in lower symmetry space groups were, however, not better. We believe

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones

• Flavia Pop and
• Narcis Avarvari

Beilstein J. Org. Chem. 2015, 11, 1105–1111, doi:10.3762/bjoc.11.124

• ethylenedithiotetrathiafulvalene-oxazoline (EDT-TTF-Ox) donors [5][6], due to a structural disorder effect [7]. Evidence was thus provided, and confirmed later on with a second complete series of conducting salts based on the same donors [8], that the presence of chiral centers can modulate the structural disorder of radical

Indolizines and pyrrolo[1,2-c]pyrimidines decorated with a pyrimidine and a pyridine unit respectively

• Marcel Mirel Popa,
• Emilian Georgescu,
• Mino R. Caira,
• Florentina Georgescu,
• Constantin Draghici,
• Raluca Stan,
• Calin Deleanu and
• Florea Dumitrascu

Beilstein J. Org. Chem. 2015, 11, 1079–1088, doi:10.3762/bjoc.11.121

• are given in Supporting Information File 1. Structural refinements were non-routine owing to subtle disorder occurring in both crystals. Taking into account the values of Z (the number of molecules per unit cell) for the crystals of 6 and 8, their respective space groups, P21/n and P−1, require that

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

• measurements. In most cases, the fullerene molecules and solvent molecules are disordered. The disorder of fullerenes and solvents cannot be suppressed even at low temperature, and can thus be characterized as having statistic rather than rotational disorder. The selected crystallographic data are summarized

Design, synthesis and photochemical properties of the first examples of iminosugar clusters based on fluorescent cores

• Mathieu L. Lepage,
• Antoine Mirloup,
• Manon Ripoll,
• Fabien Stauffert,
• Anne Bodlenner,
• Raymond Ziessel and
• Philippe Compain

Beilstein J. Org. Chem. 2015, 11, 659–667, doi:10.3762/bjoc.11.74

• chaperones were thus disclosed in the field of Gaucher disease, the most common lysosomal storage disorder (Figure 1) [24][25]. DNJ clusters 2 and 3 are indeed able to increase mutant β-glucocerebrosidase (GCase) residual activity levels as much as 3.3-fold in cells of Gaucher patients at micromolar

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• EDT-TTF derivatives with either one ester (in 2ac) or one cyano group (in 2bc) in ortho position to the CF3 group. 2ac crystallizes in the monoclinic system, space group P21, with one molecule in general position in the unit cell (Figure 3), affected by disorder on the ethylene bridge. On the other

• positional disorder of the fluorine atoms, at variance with the other structures described above. Furthermore, the two ester groups are not coplanar, one of them lies flat with the TTF core while the other one is almost perpendicular. Charge-transfer complex and radical cation salt The relatively low

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• orthorhombic system, space group P212121. The unit cell contains one independent molecule. The terminal sulfur atom presents an orientation disorder as denoted by two nearly identical occupation factors of 49% and 51% for S3 and S3A, respectively (Figure 2). This is most likely the result of orientation

• disorder of the molecule in the most stable trans configuration, rather than a cis–trans disorder. The bond lengths are within the expected range for thiophenic dithiol ketones [12][20]. The crystal structure is composed of pairs of side-by-side chains of ketone 1 running parallel to b. Within these bi

• present, in both molecules, an orientation disorder with occupation factors of 77 and 23% for the pair S8/S8A and 71 and 29% for the pair S1/S1A. The bond lengths of the molecule are within the expected range of values for neutral TTF derivatives [11]. The crystal structure is composed of layers of side

Attempts to prepare an all-carbon indigoid system

• Şeref Yildizhan,
• Henning Hopf and
• Peter G. Jones

Beilstein J. Org. Chem. 2015, 11, 363–372, doi:10.3762/bjoc.11.42

• observed (H5···π 2.76 Å, H9A···π 2.83 Å). The structure determination of 25 was of limited accuracy because of twinning and disorder problems (indeed, there may be a small amount of contamination by 24) and we therefore do not discuss it in detail. Both independent molecules display non-crystallographic

Novel biphenyl-substituted 1,2,4-oxadiazole ferroelectric liquid crystals: synthesis and characterization

• Mahabaleshwara Subrao,
• Dakshina Murthy Potukuchi,
• Girish Sharada Ramachandra,
• Poornima Bhagavath,
• Sangeetha G. Bhat and
• Srinivasulu Maddasani

Beilstein J. Org. Chem. 2015, 11, 233–241, doi:10.3762/bjoc.11.26

• phase is also noticed in the 13b (C12.Ox.C*Cn) series along with the 1D orthogonal SmA phase. Due to the presence of long chains on both sides of the oxadiazole core, the molecules are argued to favour [44][45][46] the orientational disorder, which leads to the stabilization of tilt layered structures

• orientational disorder in chiral LCs with flexible end chain on both sides. It is noticed that the isotropic temperatures are higher for the 13b (C12.Ox.C*Cn) series than the other phenyl substituted 13a homologs. Higher clearing temperatures are argued due to the chain geometry and close packing of the

Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

• Lee Trollope,
• Dyanne L. Cruickshank,
• Terence Noonan,
• Susan A. Bourne,
• Milena Sorrenti,
• Laura Catenacci and
• Mino R. Caira

Beilstein J. Org. Chem. 2014, 10, 3136–3151, doi:10.3762/bjoc.10.331

• presence of guest disorder in two cases. An account of the key features of the inclusion of the RSV molecule within the respective host cavities as well as descriptions of the crystal packing arrangements follows. The asymmetric unit of the complex TMA·RSV·6.25H2O, namely two TMA molecules, two RSV

• longer axis of each macrocycle being approximately parallel to the planes of the respective included 4-hydroxyphenyl rings. In addition, the crystallographically independent TMA host molecules adopt somewhat different conformations given the fact that their contents differ, owing to the disorder

• )°], reflecting a more ‘closed’ primary side. Regarding the mode of guest inclusion, the angle between the mean plane of the RSV molecule and the mean O4-plane of the host molecule A is ca. 85.6°, with that between the RSV major disorder component B and the mean O4-plane of host molecule B being virtually the

Mono- and multilayers of molecular spoked carbazole wheels on graphite

• Stefan-S. Jester,
• A. Vikas Aggarwal,
• Daniel Kalle and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 2783–2788, doi:10.3762/bjoc.10.295

• is fitted to match the MSW orientation (by rotation). The corners of adjacent hexagons are connected by solid black lines to form triangles and tetragons, the variation of the shapes of which points out the high degree of disorder. (f) The data obtained in (d) and (e) is translated into a

Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens

• Véronique Nardello-Rataj and
• Loïc Leclercq

Beilstein J. Org. Chem. 2014, 10, 2603–2622, doi:10.3762/bjoc.10.273

• the modified ones reached the same level after 240 min because of the formation of inclusion complexes. However, the presence of β-CD and biocide increased the disorder of cellulose microstructure and modified its mechanical properties. The bacterial activity against E. coli and S. aureus exhibited

Molecular ordering at electrified interfaces: Template and potential effects

• Thanh Hai Phan and
• Klaus Wandelt

Beilstein J. Org. Chem. 2014, 10, 2243–2254, doi:10.3762/bjoc.10.233

• /P1’ and P3/P3’) [5][6][7][13][14][15][16], as well as to an order/disorder phase transition due to chloride desorption/adsorption [17]. As mentioned in the Introduction, the viologen dication (DBV2+) is known to undergo two successive one-electron transfer steps in the electrochemical environment

Aryl substitution of pentacenes

• Andreas R. Waterloo,
• Anna-Chiara Sale,
• Dan Lehnherr,
• Frank Hampel and
• Rik R. Tykwinski

Beilstein J. Org. Chem. 2014, 10, 1692–1705, doi:10.3762/bjoc.10.178

• distances of ~3.52 Å and 3.46 Å. Pentacene 3d crystallizes in the space group P21/n with four molecules in each unit cell (Figure 8), and the thienyl and trialkylsilyl groups show disorder in the structure. With a twist angle of ~90°, the thienyl unit is essentially perpendicular to the pentacene skeleton

Synthesis of the first examples of iminosugar clusters based on cyclopeptoid cores

• Mathieu L. Lepage,
• Alessandra Meli,
• Anne Bodlenner,
• Céline Tarnus,
• Francesco De Riccardis,
• Irene Izzo and
• Philippe Compain

Beilstein J. Org. Chem. 2014, 10, 1406–1412, doi:10.3762/bjoc.10.144

• storage disorder [8][9]. In 2013, the first description of a multivalent effect for correcting protein folding defects in cells was reported with trivalent DNJ clusters [10]. These compounds were found to overcome the processing defect of the mutant CFTR protein involved in cystic fibrosis, and to be up

Novel indolin-2-one-substituted methanofullerenes bearing long n-alkyl chains: synthesis and application in bulk-heterojunction solar cells

• Irina P. Romanova,
• Andrei V. Bogdanov,
• Inessa A. Izdelieva,
• Vasily A. Trukhanov,
• Gulnara R. Shaikhutdinova,
• Dmitry G. Yakhvarov,
• Shamil K. Latypov,
• Vladimir F. Mironov,
• Vladimir A. Dyakov,
• Ilya V. Golovnin,
• Dmitry Yu. Paraschuk and
• Oleg G. Sinyashin

Beilstein J. Org. Chem. 2014, 10, 1121–1128, doi:10.3762/bjoc.10.111

• features at 550 and 600 nm indicating the lowest content of the P3HT crystalline phase. This was assigned to disorder in the P3HT crystalline phase induced by the PCBM molecules [18]. Thermal annealing of the P3HT/PCBM blend increases the content of the P3HT crystalline phase (the black curve in Figure 5

Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants^§

• Rudolf Knorr,
• Thomas Menke,
• Johannes Freudenreich and
• Claudio Pires

Beilstein J. Org. Chem. 2014, 10, 307–315, doi:10.3762/bjoc.10.28

• )-1,1,3,3-tetramethylindane (6) as the only product (97% yield). (ii) In X-ray diffraction analyses [4][5][6][7][8][9], the 1,1,3,3-tetramethylindan-2-ylidene parts turned out to be rather rigid, except for an occasional folding along the C-1/C-3 axis, and they did not exhibit the structural disorder

The difluoromethylene (CF₂) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF₂ groups

• Yi Wang,
• Ricardo Callejo,
• Alexandra M. Z. Slawin and
• David O’Hagan

Beilstein J. Org. Chem. 2014, 10, 18–25, doi:10.3762/bjoc.10.4

• -crystalline nature of 6b presumably arises due to chain disorder from linear 1,3-repulsions between the fluorines, so the preferred conformation of this motif could not be determined in this study. The melting point of palmitic acid 6c (89.9 °C) was notable in that it was significantly higher than that of the

• conformation (Figure 8). Also repulsive through space 1,4-F···F interactions will be disfavoured if the chain undergoes gauche conformational disorder. These contributing factors suggest that the 1,4-di-CF2 motif (R–CF2CH2CH2CF2–R) will be useful for adding conformational stability to aliphatic chains. The CF2

Stereoselectively fluorinated N-heterocycles: a brief survey

• Xiang-Guo Hu and
• Luke Hunter

Beilstein J. Org. Chem. 2013, 9, 2696–2708, doi:10.3762/bjoc.9.306

• [21]. For example, O’Hagan and co-workers investigated the pyrrolidine-containing molecules 9 and 10 (Figure 3) as ligands of G-quadruplex DNA [22]. The non-fluorinated ligand 9 had some conformational disorder because the pyrrolidine rings were able to interconvert between exo and endo puckers. In

• rigidifying power of a fluorine substituent is strongly dependent on the other groups present. The non-fluorinated azepane 21 was found to exhibit extensive conformational disorder, and this was attributed to competing preferences for the OBn/N3 substituents to adopt pseudoequatorial positions and for the

• preferred over the equatorial conformation (9.2 kcal/mol) because of two stabilising C–F…N+ interactions. An X-ray structure of 24 was also obtained (Figure 7), and it revealed a geometry consistent with the calculated minimum-energy structure, with no evidence of disorder. So far in this review, we have