1,3-Dibromo-5-Dodecyl-4H-Thieno[3,4-C]Pyrrole-4,6(5H)-Dione
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HS Code |
310919 |
| Chemical Formula | C18H25Br2NO2S |
| Molecular Weight | 467.27 |
| Appearance | Solid (predicted based on similar compounds) |
| Solubility | Soluble in organic solvents like dichloromethane, chloroform (common for similar organic compounds) |
| Vapor Pressure | Very low (expected for a solid organic compound) |
| Stability | Stable under normal conditions, but may react with strong oxidizing agents (general behavior of such organic molecules) |
As an accredited 1,3-Dibromo-5-Dodecyl-4H-Thieno[3,4-C]Pyrrole-4,6(5H)-Dione factory, we enforce strict quality protocols—every batch undergoes rigorous testing to ensure consistent efficacy and safety standards.
| Packing | 10 grams of 1,3 - Dibromo - 5 - Dodecyl - 4H - Thieno[3,4 - c]Pyrrole - 4,6(5H)-Dione in sealed vial. |
| Shipping | 1,3 - Dibromo - 5 - Dodecyl - 4H - Thieno[3,4 - c]Pyrrole - 4,6(5H)-Dione is shipped in accordance with chemical transport regulations. Packed securely in suitable containers to prevent leakage, ensuring safe transit for its chemical nature. |
| Storage | Store 1,3 - Dibromo - 5 - Dodecyl - 4H - Thieno[3,4 - c]Pyrrole - 4,6(5H)-Dione in a cool, dry place away from direct sunlight. Keep it in a tightly sealed container to prevent exposure to moisture and air, which could potentially cause degradation. Store it separately from incompatible substances to avoid chemical reactions. |
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In bulk heterojunction photovoltaic cells processed via slot-die coating on flexible PET/ITO substrates, the electron-deficient thieno[3,4-c]pyrrole-4,6(5H)-dione (TPD) core with 1,3-dibromo substitution delivers the necessary reactivity for Stille cross-coupling polycondensation. The dodecyl solubilizing chain attached to the imide nitrogen ensures the resulting donor–acceptor copolymer remains processable from non-halogenated solvents such as o-xylene or anisole at total solids loadings up to 25 mg mL⁻¹. Prior to polymerization, the monomer is recrystallized twice from anhydrous n-heptane and subsequently zone-refined under a dynamic vacuum of 10⁻⁶ mbar at 135 °C using a home-built horizontal gradient sublimator with 4-zone temperature control. Purity verified by analytical HPLC on a C18 column with acetonitrile/tetrahydrofuran (85:15 v/v) mobile phase must reach ≥99.8 area-% with halogen content confirmed by Schoeniger combustion followed by ion chromatography to fall within ±0.3% of the theoretical bromine mass fraction of 35.45 wt-%. Condensation polymerization with a distannyl-functionalized benzodithiophene comonomer (e.g., 2,6-bis(trimethylstannyl)-4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene) is executed in anhydrous chlorobenzene under argon in a three-necked Morton flask equipped with a condensate trap cooled to -78 °C. The catalyst system Pd₂(dba)₃ (2 mol-%) and tri(o-tolyl)phosphine (8 mol-%) is introduced via syringe after degassing the monomer mixture through three freeze-pump-thaw cycles to a residual pressure below 0.5 mbar. A monomer feed ratio of dibromide to distannyl of 1.000:1.005 compensates for protodestannylation, and the solution is heated to 110 °C for 36 h under vigorous mechanical stirring at 400 rpm. End-capping is performed by sequential addition of 2-(tributylstannyl)thiophene and 2-bromothiophene, each allowed to react for 2 h. The crude copolymer is precipitated into vigorously stirred methanol acidified with 1 vol-% concentrated HCl, collected on a 0.45 µm PTFE membrane, and subjected to sequential Soxhlet extraction with methanol, acetone, hexane, and finally chloroform. The chloroform fraction is concentrated and re-precipitated into methanol, yielding a fibrous solid. Number-average molecular weight (Mₙ) determined by high-temperature GPC at 150 °C in 1,2,4-trichlorobenzene versus narrow polystyrene calibrants is typically 32 000–48 000 g mol⁻¹ with a dispersity Đ below 2.4. For device evaluation, the copolymer is blended with PC₇₁BM in a 1:1.4 wt/wt ratio and dissolved in o-xylene containing 2 vol-% 1,8-diiodooctane at a total solids concentration of 20 mg mL⁻¹. The active layer is doctor-bladed onto ITO/ZnO substrates at a coating speed of 40 mm s⁻¹ with a gap height of 60 µm, yielding a dry film thickness of 105–115 nm verified by stylus profilometry (Dektak XT). Thermal annealing at 110 °C for 8 min on a digitally controlled hotplate inside a nitrogen-filled glovebox (O₂ <10 ppm, H₂O <5 ppm) optimizes phase separation. Completed inverted devices with MoOₓ/Ag top electrodes exhibit a certified power conversion efficiency of 10.1% under AM 1.5G illumination (Class AAA solar simulator, source calibrated against a KG5-filtered Si reference celltraceable to NREL per IEC 60904-3:2019). The short-circuit current density matches external quantum efficiency integration within 3% according to ASTM E1021-15. A critical moisture-sensitivity constraint governs monomer storage: exposure to relative humidity above 35% for more than 6 h triggers debromination observable as a shift in the aromatic proton signals in ¹H NMR (CDCl₃, 600 MHz), accompanied by a 15–20% reduction in Mₙ of the resulting polymer. Containers must remain sealed under argon with molecular sieve 3A desiccant and inventoried by Karl Fischer coulometric titration on withdrawn samples every 60 days. Can the Long Alkyl Chain Suppress Bias-Stress Instability in Solution-Sheared n-Channel Thin Films?Fabrication of n-type organic field-effect transistors (OFETs) from the dibromo TPD derivative typically involves conversion into a homopolymer or alternating copolymer via Yamamoto-type reaction with bis(1,5-cyclooctadiene)nickel(0) in dry DMF at 80 °C. The monomer is reacted with a stoichiometric equivalent of Ni(COD)₂ and 2.2 equivalents of 2,2′-bipyridine under strict Schlenk conditions, and after 48 h the product is purified by repetitive precipitation from tetrahydrofuran into methanol/acetone (1:1 v/v). The resulting polymer with a degree of polymerization near 35 repeat units shows a lowest unoccupied molecular orbital (LUMO) energy of -3.95 eV as determined by cyclic voltammetry with ferrocene internal standard (scan rate 50 mV s⁻¹, 0.1 M tetrabutylammonium hexafluorophosphate in acetonitrile). For thin-film transistor evaluation, a 5 mg mL⁻¹ solution in 1,2-dichlorobenzene is heated to 70 °C and shear-coated onto octadecyltrichlorosilane-treated SiO₂/Si substrates with a blade gap of 100 µm and substrate temperature of 60 °C. The shear speed of 0.5 mm s⁻¹ promotes edge-on crystallite orientation confirmed by grazing-incidence wide-angle X-ray scattering showing a lamellar stacking distance of 2.54 nm along the out-of-plane direction. Source and drain gold electrodes (40 nm thick) are thermally evaporated through a shadow mask defining a channel length of 50 µm and width of 1000 µm. Device characterization in nitrogen ambient using a semiconductor parameter analyzer (Keysight B1500A) yields an average electron mobility of 0.12 cm² V⁻¹ s⁻¹ extracted from the saturation regime and a threshold voltage of +4.5 V. The critical performance metric is the bias-stress instability index: after applying a constant gate voltage of +30 V for 3600 s, the drain current decay is limited to 8% of its initial value, which is attributed to the dense interdigitation of dodecyl side chains preventing water diffusion to the dielectric interface. Operation in ambient air ( 45% RH) without encapsulation leads to significant mobility degradation within 20 min; an electron-withdrawing encapsulation layer such as Cytop CTL-809M is required. The fabrication sequence is sensitive to particulate contamination on the gate dielectric — a cleanroom class ISO 5 environment is recommended during shear coating to avoid local disruption of molecular alignment.
Constructing a purely organic nanoporous framework for selective CO₂ capture utilizes the rigid dibromo monomer in a Yamamoto homocoupling scheme yielding a conjugated microporous polymer (CMP) network. The monomer is dispersed in anhydrous N,N-dimethylformamide containing 1.5 equivalents of bis(1,5-cyclooctadiene)nickel(0), 2.0 equivalents of 2,2′-bipyridine, and 1.6 equivalents of 1,5-cyclooctadiene under argon. The mixture is heated to 85 °C for 72 h inside a Parr pressure vessel to prevent solvent evaporation and maintain a homogeneous catalyst distribution. After quenching with concentrated HCl, the precipitate is washed sequentially with water, tetrahydrofuran, and chloroform, then subjected to Soxhlet extraction with methanol for 48 h and finally activated under high vacuum (10⁻⁵ mbar) at 120 °C for 12 h to yield a fine dark-brown powder. The Brunauer-Emmett-Teller specific surface area evaluated by nitrogen physisorption at 77 K on a Quantachrome Autosorb iQ reaches 910 m² g⁻¹ with a median pore width centered at 1.2 nm derived from nonlocal density functional theory. Single-component gas uptake measured at 273 K and 1 bar shows CO₂ adsorption of 2.8 mmol g⁻¹ and an ideal CO₂/N₂ selectivity of 58 calculated from initial slope ratios according to the Henry’s law method. Breakthrough experiments performed on a custom-built fixed-bed column packed with 600 mg of CMP at a total feed flow of 10 mL min⁻¹ (CO₂:N₂ = 15:85 v/v) demonstrate a breakthrough time of 420 s, decreasing to 380 s after ten sequential adsorption-desorption cycles when regeneration is conducted by heating to 110 °C under helium purge. The network retains structural integrity after 5 wt-% loading into a poly(ether-block-amide) (Pebax 1657) matrix; mixed-matrix membranes cast on a polyacrylonitrile support exhibit a CO₂ permeance of 230 GPU and maintain selectivity above 45 in 40-hour tests at 2 bar feed pressure. A processing note: the dibromide monomer must be sieved through a 200-mesh screen before charging to prevent agglomerates that cause local catalyst depletion and yield carbonized domains that reduce total pore volume by up to 12%. Red-Emitting Fluorophore Platform for Bioorthogonal LabellingThe dibromo intermediate serves as a modular building block for synthesizing donor–acceptor–donor (D–A–D) fluorophores with emission maxima situated in the phototherapeutic window. Palladium-catalyzed Suzuki-Miyaura cross-coupling with (4-(diphenylamino)phenyl)boronic acid pinacol ester proceeds in toluene/water biphasic medium with tetrakis(triphenylphosphine)palladium(0) (4 mol-%) and aqueous K₂CO₃ (2 M) heated to 90 °C for 16 h. Chromatographic purification on silica gel with hexane/dichloromethane (1:1 v/v) yields the target D–A–D compound as a red solid in 72% isolated yield after recrystallization from ethanol. The compound absorbs at 512 nm and emits at 648 nm in tetrahydrofuran (quantum yield Φ = 0.47 versus cresyl violet standard in methanol, per IUPAC guidelines). For live-cell imaging probes, the fluorophore is encapsulated into DSPE-mPEG₂₀₀₀ micelles by thin-film hydration and passage through a 0.2 µm polycarbonate membrane extruder; hydrodynamic diameter measured by dynamic light scattering remains below 45 nm with polydispersity index 0.12 after 21 days in phosphate-buffered saline at 4 °C. Confocal microscopy on HeLa cells incubated with 10 µg mL⁻¹ of the micellar formulation for 2 h reveals cytoplasmic localization with negligible dark toxicity (MTT assay viability >92%). The dodecyl chain facilitates stable intercalation into the phospholipid corona without rapid fluorophore leakage, a failure mode commonly observed with unsubstituted TPD derivatives. Note that preparative-scale Suzuki coupling with this sterically hindered dibromide requires anaerobic chamber oxygen levels below 5 ppm; higher O₂ promotes homocoupling of the boronic ester and reduces the target product yield by more than 30%. The compound functions as a reactive flame-retardant diluent in brominated epoxy resin formulations for printed circuit board laminates when blended with a bisphenol-A diglycidyl ether (DGEBA) resin and cured with stoichiometric dicyandiamide. At a loading of 12 phr, the dibrominated TPD derivative reduces the average heat release rate measured by cone calorimetry (ASTM E1354-22a) at 50 kW m⁻² irradiance by 34% relative to an equivalent stoichiometry using tetrabromobisphenol A, attributed to the thienopyrroledione heterocycle acting as a charring promoter. The prepregs achieve a UL 94 V-0 rating at 1.2 mm thickness after curing at 175 °C for 45 min; glass transition temperature (T₉) determined by dynamic mechanical analysis (DMA, 1 Hz, 3 °C min⁻¹ ramp) is 152 °C. The laminate’s comparative tracking index (CTI) measured per IEC 60112 exceeds 500 V, satisfying the minimum for Pollution Degree 2 environments. A persistent processing concern is the slow dissolution rate of the crystalline dibromide in the epoxy resin at 70 °C — pre-dissolution in methyl ethyl ketone (95 wt-% MEK) under high-shear mixing at 3000 rpm for 20 min is mandatory to eliminate crystalline inclusions that act as stress concentrators during thermal cycling between -40 °C and 125 °C per IPC-TM-650 2.6.7.1. The bromine release threshold during smoldering combustion exceeds 1500 ppm in the gas phase, mandating extraction ventilation compliant with DIN EN 14175 during laminate curing. |
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The electron-deficient heterocyclic monomer 1,3-dibromo-5-dodecyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (commonly designated TPD-Br2-C12 or DTTPD-C12 dibromide) functions as a cornerstone acceptor building block in donor–acceptor (D–A) conjugated copolymers engineered for bulk-heterojunction organic photovoltaic (OPV) active layers, organic field-effect transistor (OFET) semiconductors, and perovskite interfacial charge-transporting layers. The planar thieno[3,4-c]pyrrole-4,6-dione (TPD) core bears two bromine atoms at the 1- and 3-positions, sites that undergo palladium-catalysed Stille or Suzuki cross-coupling with distannyl- or diboronic ester-functionalized donor segments, while the N-5 position is functionalized with a linear n-dodecyl substituent to modulate solubility, chain packing, and thin-film morphology. The monomer’s symmetry and strong electron-withdrawing imide groups lower the lowest unoccupied molecular orbital (LUMO) of the resultant copolymers to approximately −3.7 eV (versus vacuum), a range critical for efficient electron transfer to fullerene or non-fullerene acceptors in OPV devices certified under IEC 60904-3 spectral conditions.
IUPAC designation: 1,3-dibromo-5-dodecyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione. Empirical formula C₂₂H₃₁Br₂NO₂S, molecular weight 533.36 g·mol⁻¹. The compound is isolated as an off-white to pale yellow crystalline powder with a melting endotherm recorded by differential scanning calorimetry at 78–80 °C (heating rate 10 °C·min⁻¹, under nitrogen, method conforming to ASTM E794-06(2018)). High-performance liquid chromatography (HPLC) on an Agilent 1260 Infinity II system equipped with a Zorbax Eclipse XDB-C18 column and UV detection at 254 nm indicates an area-percent purity ≥ 98.5% (quantitation per ASTM E2036-16). Residual halide contaminants determined by suppressed ion chromatography (EN ISO 10304-1) are maintained below 100 ppm chloride and 50 ppm bromide, as free halide ions can poison palladium catalysts during polymerization. Total metal content, assessed by inductively coupled plasma mass spectrometry following closed-vessel acid digestion (EPA Method 200.8), is specified at ≤ 50 ppm, essential to avoid undesired conductive pathways in final semiconductor films.
A critical differentiator among 4H-thieno[3,4-c]pyrrole-4,6(5H)-dione dibrominated monomers lies in the N-alkyl substituent. The dodecyl chain (C₁₂H₂₅) imparts a solubility window in chlorobenzene and o-dichlorobenzene that enables homogeneous Stille polycondensation at monomer concentrations up to 0.2 M without premature precipitation, a limitation frequently encountered with hexyl (C₆) or 2-ethylhexyl branched analogs. This solubility margin permits higher molecular weight build-up before the reaction mass vitrifies or gels, directly influencing film-forming capability and charge-transport properties in the final polymer.
When processed under identical Stille cross-coupling conditions—2 mol% tris(dibenzylideneacetone)dipalladium(0) and 8 mol% tri(o-tolyl)phosphine in anhydrous chlorobenzene at 110 °C—the dodecyl-substituted monomer yields poly(TPD-alt-bithiophene) with a number-average molecular weight (Mn, by gel permeation chromatography against polystyrene standards, ASTM D5296-19) in the range 45–65 kDa and polydispersity 2.0–2.5. The hexyl-substituted analogue, in contrast, typically precipitates before reaching 25 kDa, with broad polydispersity exceeding 3.5, while the branched 2-ethylhexyl congener gives intermediate Mn values of 30–38 kDa. These differences in polymer molecular weight cascade into film morphology: atomic force microscopy of blends with [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) at a 1:1.5 weight ratio reveals root-mean-square roughness (Rq) of 1.2 nm for the dodecyl-based polymer, compared with 4.8 nm for the hexyl analog and 2.3 nm for 2-ethylhexyl. Reduced phase separation is consistent with the dodecyl chain’s ability to plasticise the amorphous intermixed phase without sacrificing crystallinity. The table below summarizes key comparative data, measured on polymers synthesized under analogous conditions and processed from chlorobenzene solutions.
| Property | TPD-C12 (dodecyl) | TPD-C6 (hexyl) | TPD-2EH (2-ethylhexyl) |
|---|---|---|---|
| Mn (kDa, GPC ASTM D5296-19) | 52 | 18 | 35 |
| PDI | 2.1 | 3.8 | 2.6 |
| Solubility in chlorobenzene (mg·mL⁻¹, 25 °C) | 35 | 4 | 16 |
| HOMO (eV, CV vs. Fc/Fc⁺) | −5.42 | −5.47 | −5.44 |
| LUMO (eV, CV) | −3.72 | −3.70 | −3.71 |
| Blend RMS roughness Rq (nm, AFM 5 µm × 5 µm) | 1.2 | 4.8 | 2.3 |
| OPV PCEmax (%) (AM1.5G IEC 60904-3) | 8.9 | 3.2 | 6.1 |
When 1,3-dibromo-5-dodecyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione is copolymerized with an electron-rich donor unit such as benzo[1,2-b:4,5-b′]dithiophene (BDT), the resulting alternating copolymer tends to adopt a mixed face-on/edge-on orientation in thin films, as evidenced by grazing-incidence wide-angle X-ray scattering (GIWAXS). The (100) lamellar packing distance shifts from 21.3 Å in the hexyl-substituted polymer to 24.8 Å in the dodecyl derivative, while the π–π stacking distance remains practically unchanged at 3.6 Å, confirming that the longer linear chain expands inter-lamellar spacing without disrupting the electronic coupling integral to charge transport. This subtle modulation of paracrystalline order is exploited to fine-tune percolation pathways in non-fullerene acceptor blends where excessive domain purity otherwise limits exciton dissociation efficiency.
Stille polycondensation of TPD-Br2-C12 with 5,5′-bis(trimethylstannyl)-2,2′-bithiophene proceeds under rigorous anhydrous and oxygen-free conditions. In a representative procedure executed on a 100 mL Schlenk tube fitted with a Teflon-coated oval stir bar and an oil bubbler, both monomers (0.3 mmol each) are dissolved in 8 mL of anhydrous chlorobenzene within an MBraun glovebox (O₂ < 1 ppm, H₂O < 1 ppm). The monomer solution is pre-dried over activated 3 Å molecular sieves for 24 h prior to use, and the monomer itself is dried in a vacuum oven at 60 °C for 2 h (0.1 mbar) immediately before charging. Omitting this drying step results in Mn below 20 kDa due to imide hydrolysis under Pd catalysis, a failure mode routinely encountered when ambient humidity exceeds 60 % RH. After addition of Pd₂(dba)₃ (0.006 mmol) and P(o-tol)₃ (0.024 mmol), the mixture is subjected to three freeze–pump–thaw cycles, backfilled with argon, and heated to 110 °C for 48 h. The viscosity increases markedly after 24 h; an additional 5 mL of anhydrous chlorobenzene is introduced via syringe through a septum cap to maintain stirrability. End-capping is performed with 2-bromothiophene (0.1 mmol) for 2 h followed by 2-(tributylstannyl)thiophene (0.1 mmol) for a further 2 h. The crude polymer is precipitated into methanol, collected by filtration, and purified by sequential Soxhlet extraction with acetone (12 h), hexane (12 h), and chloroform (24 h). The chloroform fraction yields the target polymer in isolated yields of 70–85%.
Electronic-grade monomer quality is defined by thresholds that directly govern device reliability and batch-to-batch consistency. The table below collates the specifications applied to TPD-Br2-C12 lots destined for conjugated polymer synthesis, each parameter anchored to an established analytical methodology. Halide and metal limits are set by correlation with dark current density and trap-assisted recombination observed in completed single-carrier devices: residual chloride above 100 ppm in the monomer has been associated with an increase in shunt losses of more than 15% in OPV cells, ascribed to ionic migration under illumination.
| Parameter | Specification | Test Method |
|---|---|---|
| Purity (area %) | ≥ 98.5 | ASTM E2036-16 / HPLC-UV (254 nm) |
| Melting point | 78 – 80 °C | ASTM E794-06(2018) (DSC, 10 °C·min⁻¹, N₂) |
| Ionic chloride (Cl⁻) | ≤ 100 ppm | EN ISO 10304-1 (suppressed IC) |
| Ionic bromide (Br⁻) | ≤ 50 ppm | EN ISO 10304-1 |
| Total metals (Cr, Fe, Ni, Cu, Zn, Pd) | ≤ 50 ppm | EPA 200.8 (ICP-MS, acid digestion) |
| Solubility in anhydrous chlorobenzene (25 °C) | ≥ 100 mg·mL⁻¹ | Gravimetric, 0.2 µm PTFE filtration |
| Appearance | Off-white crystalline powder | Visual inspection under D65 illumination |
The monomer is packaged under argon in amber glass vials sealed with PTFE-lined caps; long-term storage is recommended at −20 °C with desiccant. Opening in ambient atmosphere must not exceed 15 minutes cumulative exposure, as the imide ring is susceptible to hydrolysis at relative humidity above 60%. Re-drying under vacuum at 60 °C for 2 h restores material that has been exposed to brief moisture ingress, but oxidative degradation products—detectable as a yellow-brown discoloration—render the monomer unsuitable for controlled polymerizations, as they introduce ill-defined end-groups and accelerate catalyst deactivation.
