Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

• John A. Love,
• Shu-Hua Chou,
• Ye Huang,
• Guilllermo C. Bazan and
• Thuc-Quyen Nguyen

Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249

• extraction, it significantly reduces the magnitude of the effects, removing the dramatic s-shape of the curve. Thin film X-ray diffraction Changes in device performance upon addition of solvent additives are typically ascribed to improvements in the BHJ nanostructure by affecting the thermodynamics and

• behavior of the two blends dynamic secondary ion mass spectrometry (DSIMS) was employed. In DSIMS, a sample is bombarded with ions, ablating ionized material, which is analyzed using a mass spectrometer [65]. The composition of the ablated material is monitored as the beam mills through the thin film

A self-assembled cyclodextrin nanocarrier for photoreactive squaraine

• Ulrike Kauscher and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2016, 12, 2535–2542, doi:10.3762/bjoc.12.248

• . Amphiphilic β-cyclodextrins substituted with 7 dodecylsulfide groups on the primary side and 7 oligo(ethylene glycol) units on the secondary side were obtained via a straightforward three step synthesis as described [27][30]. A thin film of these amphiphiles was obtained by evaporation of a chloroform

High performance p-type molecular electron donors for OPV applications via alkylthiophene catenation chromophore extension

• Paul B. Geraghty,
• Calvin Lee,
• Jegadesan Subbiah,
• Wallace W. H. Wong,
• James L. Banal,
• Mohammed A. Jameel,
• Trevor A. Smith and
• David J. Jones

Beilstein J. Org. Chem. 2016, 12, 2298–2314, doi:10.3762/bjoc.12.223

• optical microscopy (POM). POM was utilized in conjunction with a heating platform to directly observe these phase transitions and elucidate thin film structure. On heating at 10 °C·min−1 BQR shows a single phase transition to the isotropic melt at 202 °C, while on cooling we have identified an initial

• appearance of long needle like crystal forms in the POM images obtained. UV–vis and fluorescence spectroscopy. Solution and thin film UV–vis absorption profiles of the BXxR are shown in Figure 4 and Figure 5, respectively, with selected data collected in Table 1 (all spectra can be found in the Supporting

• aggregates (Figure 5d). Side-chain modification from butyl to octyl in the BT4R, BTR and BT8R series also impacts on the thin film formation as seen in as-cast films with poor development of the crystalline order in BT4R and BT8R, as well as a λmax blue-shift of both BTXR analogues, when compared to BTR

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

• thin-film microstructure playing such a key role in the optoelectronic and charge transport properties of conjugated polymers, block copolymers naturally appear as useful tools for tailoring the thin-film morphology [1][2][3][4][5]. The propensity of some block copolymers to phase segregate at the nano

• of thin films spin-cast from hot 1,2,4-trichlorobenzene were measured. The thin film UV–visible absorption of polythiophene derivatives can provide some information about the molecular order of the polymer chains, via the interpretation of the vibronic shoulders [52][53][54][55]. In the case of

• interpretation of the vibronic structure in relation to the order in the thin film, it is worth noting that the vibronic structure of the block copolymers in both cases is less pronounced than for the corresponding blend. Considering the aformentioned link between the vibronic structure and aggregation, this

A flow reactor setup for photochemistry of biphasic gas/liquid reactions

• Josef Schachtner,
• Patrick Bayer and
• Axel Jacobi von Wangelin

Beilstein J. Org. Chem. 2016, 12, 1798–1811, doi:10.3762/bjoc.12.170

• simple commercial components. This paper describes in full detail the nature and function of the required building elements, the assembly of parts, and the tuning and interdependencies of the most important reactor and reaction parameters. Unlike many commercial thin-film and microchannel reactors, the

• ], multiphasic reactions including solid-phase protocols [18], addition of gaseous reagents [19], high-pressure conditions [20], cascade conversions without intermediate work-up operations [21], as well as thin film, falling film [22], micro-channel [23], and tube-in-tube reactors [24][25] for reactions between

• reported herein differs from most of the known systems in some key characteristics. Small-dimensioned thin film/falling film and microchannel reactors allow residence times in the seconds-to-few-minute range, which holds great potential for rapid conversions but is unsuitable for the significantly slower

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

• , the hole mobility of these compounds in blended films was measured using the space-charge-limited current method (SCLC). The device structure studied here was ITO/PEDOT:PSS/COOP-nHT-TBDT:PC61BM/MoO3/Al, and the thin film deposition method is similar to that for solar cell fabrication. The analysis

Synthesis and characterization of benzodithiophene and benzotriazole-based polymers for photovoltaic applications

• Desta Gedefaw,
• Marta Tessarolo,
• Margherita Bolognesi,
• Mario Prosa,
• Renee Kroon,
• Wenliu Zhuang,
• Patrik Henriksson,
• Kim Bini,
• Ergang Wang,
• Michele Muccini,
• Mirko Seri and
• Mats R. Andersson

Beilstein J. Org. Chem. 2016, 12, 1629–1637, doi:10.3762/bjoc.12.160

• optical characterization, both in solution and thin-film, indicated that PTzBDT-1 has a red-shifted optical absorption compared to PTzBDT-2, likely due to a more planar conformation of the polymer backbone promoted by the lower content of alkyl side chains. The different aggregation in the solid state

• energies [31]. Finally, the resulting thin-film quality, and subsequent polymer self-organization, prepared over the electrode or over a flat substrate might be different, reflecting possible variations. Photovoltaic properties A set of BHJ solar cells, using PTzBDT-1 and PTzBDT-2 as donors and PC61BM as

• spin-coated respectively from 1,2,4-trichlorobenzene (TCB) and 1,2-dichlorobenzene (ODCB) solutions (best solvents in terms of solubility and thin-film quality for each polymer) without the need of additional processing solvent additives. All the details for the fabrication and characterization of the

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

• state. The optical band gaps of TTA-DPP4 and TTA-DPP2 are estimated to be 1.64 and 1.65 eV, respectively, from the onset positions of their absorption bands. The absorption coefficient (α) of TTA-DPP4 (16.7 × 104 cm−1) in the thin film is still considerably larger than that of TTA-DPP2 (11.5 × 104 cm−1

3,6-Carbazole vs 2,7-carbazole: A comparative study of hole-transporting polymeric materials for inorganic–organic hybrid perovskite solar cells

• Wei Li,
• Munechika Otsuka,
• Takehito Kato,
• Yang Wang,
• Takehiko Mori and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2016, 12, 1401–1409, doi:10.3762/bjoc.12.134

• properties The UV–vis absorption spectra were employed to evaluate the optical properties of 3,6-Cbz-EDOT and 2,7-Cbz-EDOT. The spectra were measured in CH2Cl2 and in thin films (spin-coated on an ITO glass). The absorption maximum (λmax) of 3,6-Cbz-EDOT in CH2Cl2 was 362 nm, whereas the thin film showed the

• bathochromically-shifted λmax at 374 nm (Figure 1a). Compared to 3,6-Cbz-EDOT, 2,7-Cbz-EDOT showed a lower energy absorption in both the solution and thin film states (λmax = 435 nm in CH2Cl2; λmax = 443 nm in the thin film), which is consistent with previous reports [26]. The red shifts in the absorption spectra

• from the solution to thin film states implied the presence of strong intermolecular interactions between the polymer backbones. Cyclic voltammetry (CV) of the polymer thin films was measured in CH3CN with 0.1 M (n-C4H9)4NPF6 as the supporting electrolyte at 20 °C. Both polymers displayed irreversible

Separation and identification of indene–C₇₀ bisadduct isomers

• Bolong Zhang,
• Jegadesan Subbiah,
• David J. Jones and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2016, 12, 903–911, doi:10.3762/bjoc.12.88

• thin film nanostructure are key factors in determining the performance of these fullerene derivatives in BHJ solar cell devices. With the observations in this study, it can be argued that the success of IC70BA (and in extension, IC60BA) as the electron acceptor component in BHJ solar cells is

Syntheses of dibenzo[d,d']benzo[2,1-b:3,4-b']difuran derivatives and their application to organic field-effect transistors

• Minh Anh Truong and
• Koji Nakano

Beilstein J. Org. Chem. 2016, 12, 805–812, doi:10.3762/bjoc.12.79

• −5 cm2·V−1·s−1 and an Ion/Ioff ratio of 101, while those with HMDS-treated substrates demonstrated higher mobility of 1.5 × 10−3 cm2·V−1·s−1 with an Ion/Ioff ratio of 103. The deposition of syn-DBBDF 5 at Tsub = 60 °C did not give a thin film, which should be caused by re-sublimation of syn-DBBDF 5

• ), respectively. The FET performance also depends on the substrate temperature during thin-film fabrication. Thus, the highest hole mobility of 1.0 × 10−1 cm2·V−1·s−1 was obtained for the syn-DNBDF-based device fabricated on the HMDS-treated substrate at Tsub = 90 °C, while it was lower than that fabricated with

• anti-DNBDF derivatives [39]. Analysis of thin films The vapor-deposited thin films of syn-DBBDF 5 and syn-DNBDF 6 were analyzed by X-ray diffraction (XRD) and atomic force microscopy (AFM). Figure 6 shows the out-of-plane XRD pattern and an AFM image of the thin film of syn-DNBDF 6 on the HMDS-treated

Thermal and oxidative stability of Atlantic salmon oil (Salmo salar L.) and complexation with β-cyclodextrin

• Daniel I. Hădărugă,
• Mustafa Ünlüsayin,
• Alexandra T. Gruia,
• Cristina Birău (Mitroi),
• Gerlinde Rusu and
• Nicoleta G. Hădărugă

Beilstein J. Org. Chem. 2016, 12, 179–191, doi:10.3762/bjoc.12.20

• a temperature-controlled oven (Nabertherm L1/12, Lilienthal, Germany) in air at atmospheric pressure (70% relative humidity). The ASO was uniformly distributed on the bottom of the glass flask. Approximately 50 mg of fish oil were needed to obtain a thin film on a plate surface of 315 cm2. Two

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• copolymerizing the europium complex of the terpyridine monomer 51 with the carbazole-substituted norbornene 50. In solution or in thin film these Eu-containing products exhibited important metal-centered photoluminescence recommending them for novel applications. Unveiling and rationalizing the interactions

Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properties

• Xiang Sun,
• Guoqiao Lai,
• Zhifang Li,
• Yuwen Ma,
• Xiao Yuan,
• Yongjia Shen and
• Chengyun Wang

Beilstein J. Org. Chem. 2015, 11, 2343–2349, doi:10.3762/bjoc.11.255

• UV–vis spectrum of T1 (thin film on glass) before and after iodine doping. Upon exposure to iodine vapor for 30 min in a sealed container, a new absorption band was observed at approximately 850 nm, which suggested the formation of the CT complex [27]. IR spectra of TCNQ, T1/TCNQ, and T2/TCNQ are

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

• polymer thin film revealed the splitting of the first oxidation wave during the cathodic run, which the authors attributed to a stepwise reduction from the aggregated radical cation to an intermediate mixed valence state, then further reduction to the neutral species. To decrease the difference in the

• exhibited a red-shifted absorption with maxima occurring at 578 and 598 nm in CH2Cl2 and as a thin film, respectively. The CVs in CH2Cl2 solution of 35 and 37 (Table 2) revealed two quasi-reversible oxidation waves that are shifted to lower potentials compared to the corresponding reversible oxidation waves

• CS2 was used for NMR spectroscopy in these cases. For compound 54 (n = 2) the absorption spectrum as a thin film exhibits a maximum at 496 nm and is red-shifted by 35 nm compared to the solution state spectrum, suggesting strong intermolecular interactions in the solid phase. Single crystal X-ray

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• ], which demonstrated thin film charge carrier mobilities of up to 8.61 × 10−3 cm2 V−1 s−1 [11]. Crystallographic studies of the largest of these structures revealed significant twisting of the terminal thiophene units in septithiophene chains, leading to weak conjugation in this part of the molecule [14

Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

• Yunfei Wang and
• Yuming Zhao

Beilstein J. Org. Chem. 2015, 11, 957–965, doi:10.3762/bjoc.11.107

• electrochemical patterns can be seen in the cyclic voltammograms of carboxyl-DTF 7 and Zn-DTF complex 9 (Figure 2C and 2E); however, their redox potentials showed a slight degree of variation. Experimentally, the cyclic voltammogram of 9 was determined from its solid thin film compressed on the working electrode

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf₂N ionic liquid

• Andrea P. Sandoval,
• Marco F. Suárez-Herrera and
• Juan M. Feliu

Beilstein J. Org. Chem. 2015, 11, 348–357, doi:10.3762/bjoc.11.40

• of PEDOT thin films synthesized on a) Pt(111), b) Pt(100) and c) Pt(110) with a charge density of 1.2 mC cm−2. The film thickness is approximately 10 nm. In situ FTIR spectra of a PEDOT thin film synthesized with a charge density of 0.6 mC cm−2 on Pt(111). 250 interferograms were recorded per

• spectrum. The reference potential was −0.90 V. a) p-Polarized spectrum at 0.80 V. b) s-Polarized spectrum at 0.80 V. c) ATR spectrum of 0.1 M [EMMIM]Tf2N in acetonitrile, obtained as the average of 100 interferograms. a) In situ FTIR spectra of a PEDOT thin film synthesized with a charge density of 0.6 mC

Photovoltaic-driven organic electrosynthesis and efforts toward more sustainable oxidation reactions

• Bichlien H. Nguyen,
• Robert J. Perkins,
• Jake A. Smith and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2015, 11, 280–287, doi:10.3762/bjoc.11.32

• reaction solution is flowed as a thin film between two closely spaced electrodes. The small separation between the electrodes enables the charged molecules generated at each electrode to interact. This neutralizes the charges, reduces the resistance of the cell, and eliminates the need for an electrolyte

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• 10 (red) in solution (left) and thin-film (right). The experiments in solution were carried out in dichloromethane (0.1 mM) using a glassy carbon electrode. A film was deposited from a solution of the triads in dichloromethane on a glassy carbon electrode and experiments were carried out in

Polyglycerol-functionalized nanodiamond as a platform for gene delivery: Derivatization, characterization, and hybridization with DNA

• Li Zhao,
• Yuki Nakae,
• Hongmei Qin,
• Tadamasa Ito,
• Takahide Kimura,
• Hideto Kojima,
• Lawrence Chan and
• Naoki Komatsu

Beilstein J. Org. Chem. 2014, 10, 707–713, doi:10.3762/bjoc.10.64

• of Spectra/Pro® dialysis membrane, MWCO: 12–14 kDa. FTIR spectral measurements were conducted using IR Prestige-21 (Shimadzu Co.). Samples were prepared by drop-coating of suspension to form a thin film on a stainless alloy plate, and then dried at 70 °C. Hydrodynamic diameters in solution were

Bis(benzylamine) monomers: One-pot preparation and application in dendrimer scaffolds for removing pyrene from aqueous environments

• Olivia N. Monaco,
• Sarah C. Tomas,
• Meghan K. Kirrane and
• Amy M. Balija

Beilstein J. Org. Chem. 2013, 9, 2320–2327, doi:10.3762/bjoc.9.266

• , which could favorably interact with the PAHs [32]. Pyrene inclusion formation constants were calculated using the measurement results obtained with the thin film experiments after two days (Table 3). The inclusion values were large, ranging from 109 to 1011 M−1, and are comparable to previous results

Synthesis of the reported structure of piperazirum using a nitro-Mannich reaction as the key stereochemical determining step

• James C. Anderson,
• Andreas S. Kalogirou,
• Michael J. Porter and
• Graham J. Tizzard

Beilstein J. Org. Chem. 2013, 9, 1737–1744, doi:10.3762/bjoc.9.200

• ) gave diamine 21 (452 mg, 85%) as a brown oil; Rf 0.50 (CH2Cl2/MeOH 10:1); IR νmax (thin film): 3374 (br, N-H), 2955 (w, C-H), 1618 (w), 1508 (s, C=C), 1465 (m), 1441 (w), 1385 (w), 1366 (w), 1292 (w), 1238 (s), 1179 (w), 1154 (w), 1038 (m), 816 (m), 752 (s) cm−1; 1H NMR (600 MHz) δ 0.90 (d, J = 6.5, 3H

• column chromatography (petrol ether/EtOAc 7:3) to give piperazinone 23 (57 mg, 69%) as a brown solid; mp 152–153 °C; Rf 0.30 (petrol ether/EtOAc 7:3); IR νmax (thin film): 3209 (br, N-H), 2956 (w, C-H), 1671 (s, C=C), 1622 (s), 1499 (s), 1464 (m), 1442 (m), 1409 (m), 1384 (m), 1366 (m), 1331 (m), 1283 (m

• flash column chromatography (petrol ether/Me2CO 4:1) to give piperazinone 25 (170 mg, 99%) as a colourless oil; Rf 0.50 (petrol ether/Me2CO 4:1); IR νmax (thin film): 3207 (br, N-H), 2954 (m, C-H), 1658 (s, C=O), 1505 (C=C), 1465 (m), 1367 (m), 1242 (s), 1180 (m), 1039 (m), 827 (m), 788 (m), 733 (m) cm

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

• Helga Seyler,
• Jegadesan Subbiah,
• David J. Jones,
• Andrew B. Holmes and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2013, 9, 1492–1500, doi:10.3762/bjoc.9.170

• with the emergence of organic electronic devices. In particular, large-area devices such as organic thin-film photovoltaics will require significant quantities of materials for device optimization, lifetime testing and commercialization. Sourcing large quantities of materials required for the

Thiourea-catalyzed Diels–Alder reaction of a naphthoquinone monoketal dienophile

• Carsten S. Kramer and
• Stefan Bräse

Beilstein J. Org. Chem. 2013, 9, 1414–1418, doi:10.3762/bjoc.9.158

• , 172.0, 151.7, 151.3, 133.4, 129.9, 126.0, 125.3, 117.7, 115.0, 109.8, 67.9, 67.6, 67.2, 61.7, 58.3, 57.3, 57.1, 52.8, 32.6, 26.0, 25.8, 23.4, 18.3, 14.3, −4.3, −4.61; IR (thin film) νmax: 1710, 1477, 1269, 1208, 1002, 959, 920, 836, 805, 776, 723 cm−1; EIMS m/z: 532.2, 487.2, 476.2, 475.2, 413.1, 403.1