Synthesis of 2,1,3‐benzothiadiazolecarbonitriles

Pilgram, K.; Skiles, Richard D.

doi:10.1002/jhet.5570110521

Cited by 18 publications

(19 citation statements)

References 4 publications

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“…Compounds 9f, 9h,a nd 10 are new compounds and their synthesis, characterization and crystallographic data are provided in the Supporting Information. Compounds 2a, [127] 2b, [128] 2c, [129] 3b, [130] 4a, [131] 4b, [132] 4c, [133] 4d, [134] 5a, [64] 5b, [60] 5c, [68] 5d, [135] 5e,a nd 7 were obtained commercially.T hese compounds were reported previously (except for 5e and 7), without crystallographic characterization. The crystals were grown or used as received, and reported for the first time in this report (see Supporting Information).…”

Section: Methodsmentioning

confidence: 99%

Chalcogen Bonding “2S–2N Squares” versus Competing Interactions: Exploring the Recognition Properties of Sulfur

Mark

Trapp

Schwab

et al. 2018

Chemistry A European J

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Chalcogen bonding (CB) is the focus of increased attention for its applications in medicinal chemistry, materials science, and crystal engineering. However, the origin of sulfur's recognition properties remains controversial, and experimental evidence for supporting theories is still emerging. Here, a comprehensive evaluation of sulfur CB interactions is presented by investigating 2,1,3‐benzothiadiazole X‐ray crystallographic structures gathered from the Cambridge Structure Database (CSD), Protein Data Bank (PDB), and own laboratory findings. Through the systematic analysis of substituent effects on a subset library of over thirty benzothiadiazole derivatives, the competing interactions have been categorized into four main classes, namely 2S–2N CB square, halogen bonding (XB), S⋅⋅⋅S, and hydrogen‐bonding (HB). A geometric model is employed to characterize the 2S–2N CB square motifs and discuss the role of electrostatic, dipole, and orbital contributions toward the interaction.

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Section: Methodsmentioning

confidence: 99%

Chalcogen Bonding “2S–2N Squares” versus Competing Interactions: Exploring the Recognition Properties of Sulfur

Mark

Trapp

Schwab

et al. 2018

Chemistry A European J

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“…38 However, to the best of our knowledge, this acceptor unit has not been incorporated into conjugated polymers. This is probably due to the harsh conditions (reflux in fuming H 2 SO 4 ) required for the electrophilic bromination of the electron poor heterocycle which are not compatible with the nitrile group.…”

Section: Synthesis Of Monomers and Polymersmentioning

confidence: 99%

Effect of Systematically Tuning Conjugated Donor Polymer Lowest Unoccupied Molecular Orbital Levels via Cyano Substitution on Organic Photovoltaic Device Performance

et al. 2016

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We report a systematic study into the effects of cyano substitution on the electron accepting ability of the common acceptor 4,7-bis(thiophen-2-yl)-2,1,3-benzothiadiazole (DTBT). We describe the synthesis of DTBT monomers with either zero, 1 or 2 cyano groups on the BT unit, and their corresponding co-polymers with the electron rich donor dithienogermole (DTG). The presence of the cyano group is found to have a strong influence on the optoelectronic properties of the resulting donor-acceptor polymers, with the optical band gap red-shifting by approximately 0.15 eV per cyano substituent. We find that the polymer electron affinity is significantly increased by ca. 0.25 eV upon addition of each cyano group, whilst the ionization potential is less strongly affected, increasing by less than 0.1 eV per cyano substituent. In organic photovoltaic (OPV) devices power conversion efficiencies (PCE) are almost doubled from around 3.5% for the unsubstituted BT polymer to over 6.5% for the mono-cyano substituted BT polymer However, the PCE drops to less than 1% for the di-cyano substituted BT polymer. These differences are mainly related to differences in the photocurrent, which varies by one order of magnitude between the best (1CN) and worst devices (2CN). The origin of this variation in photocurrent was investigated by studying the charge generation properties of the photoactive polymer:fullerene blends using fluorescence and transient absorption spectroscopic techniques. These measurements revealed that the improved photocurrent of 1CN in comparison to 0CN was due to improved light harvesting properties whilst maintaining a high exciton dissociation yield. The addition of one cyano group to the BT unit optimized the position of the polymer LUMO level closer to that of the electron acceptor PC71BM, such that the polymer's light harvesting properties were improved without sacrificing either exciton dissociation yield or device V OC . We also identify that the drop in performance for the 2CN polymer is caused by very limited yields of electron transfer from the polymer to the fullerene LUMO levels, likely caused by poor orbital energy level alignment with the fullerene acceptor (PC71BM). This work highlights the impact that small changes in chemical structure can have on the optoelectronic and device properties of semiconducting polymer. In particular this work highlights the effect of LUMO-LUMO offset on the excited state dynamics of polymer:fullerene blends.

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“…For the synthesis of the second building block, amide linker chains were introduced by converting 1 through the Rosenmund-von Braun reaction into BTD-4,7dicarbonitrile 5, [64] which was subsequently hydrolyzed to BTD-4,7-dicarboxylic acid 6. For the synthesis of the second building block, amide linker chains were introduced by converting 1 through the Rosenmund-von Braun reaction into BTD-4,7dicarbonitrile 5, [64] which was subsequently hydrolyzed to BTD-4,7-dicarboxylic acid 6.…”

Section: Resultsmentioning

confidence: 99%

“…Compound 3 was phosphitylated to 4,7-dihexynyl-BTDphosphoramidite 4. For the synthesis of the second building block, amide linker chains were introduced by converting 1 through the Rosenmund-von Braun reaction into BTD-4,7dicarbonitrile 5, [64] which was subsequently hydrolyzed to BTD-4,7-dicarboxylic acid 6. [65] Amide formation involved treatment of 6 with a 1:1 mixture of 3-hydroxypropylamine and 3-(4,4Ј-dimethoxytrityloxy)propylamine [66] to provide the mono-DMT-protected intermediate 7.…”

Section: Resultsmentioning

confidence: 99%

“…[64,65] All other compounds were synthesized as described below and analyzed by NMR spectroscopy (Bruker, 300 MHz) and mass spectrometry [LTQ Orbitrap XL; accurate mass determination with nanospray ionization (NSI) in the positive mode; acetonitrile as solvent]. [64,65] All other compounds were synthesized as described below and analyzed by NMR spectroscopy (Bruker, 300 MHz) and mass spectrometry [LTQ Orbitrap XL; accurate mass determination with nanospray ionization (NSI) in the positive mode; acetonitrile as solvent].…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

2,1,3‐Benzothiadiazole‐Modified DNA

Garo

Häner

2012

Eur J Org Chem

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The use of 2,1,3‐benzothiadiazole (BTD) as a structural element with advanced electronic properties for DNA hybrids is described. Bis(alkynyl)‐ and bis(carboxamide)‐derived BTD units are shown to support duplex stability through interstrand stacking interactions. Placement of the BTD units opposite to a natural base, however, leads to considerable destabilization. The bis(alkynyl)‐derived BTD W is strongly fluorescent, and quantum yields of up to 0.20 are observed. Its fluorescence behavior is strongly dependent on the neighboring nucleobases. The quenching effect of the natural bases decreases in the order G >> A ≥ T ≥ C and correlates very well with the free energies for charge separation (ΔGCS) through photoinduced electron transfer, as calculated by the Rehm–Weller equation. Fluorescence of W is completely quenched when it is placed against the bis(carboxamide)‐derived BTD V. The described BTD‐based compounds W and V represent valuable building blocks for the construction of highly ordered, DNA‐based materials with special optical and electronic properties.

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Synthesis of 2,1,3‐benzothiadiazolecarbonitriles

Cited by 18 publications

References 4 publications

Chalcogen Bonding “2S–2N Squares” versus Competing Interactions: Exploring the Recognition Properties of Sulfur

Chalcogen Bonding “2S–2N Squares” versus Competing Interactions: Exploring the Recognition Properties of Sulfur

Effect of Systematically Tuning Conjugated Donor Polymer Lowest Unoccupied Molecular Orbital Levels via Cyano Substitution on Organic Photovoltaic Device Performance

2,1,3‐Benzothiadiazole‐Modified DNA

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