Narrow bandgap thienothiadiazole-based conjugated porous polymers: from facile direct arylation polymerization to tunable porosities and optoelectronic properties

Abstract

Conjugated porous polymers with narrow bandgaps, tunable morphologies, porosities and optoelectronic properties are synthesized via facile direct arylation polymerization.

Tailored Band Gaps in Sulfur‐ and Nitrogen‐Containing Porous Donor–Acceptor Polymers

“…It is noteworthy that these values are among the highest of all hitherto reported sulfur‐ and nitrogen‐containing microporous polymers (Supporting Information, Table S14) . Pore size distribution (PSD) analysis shows a broad range of pore diameters between 1 and 10 nm which correlates well with the large pore windows and the complex stacking arrangements expected for these networks (Figure b).…”

Exploring the “Goldilocks Zone” of Semiconducting Polymer Photocatalysts by Donor–Acceptor Interactions

“…[3b, 20] Prepared SNPs have am oderate reversible CO 2 uptake between 0.69 to 2.04 mmol g À1 at 273 K( Figure S29 ci nt he Supporting Information);c omparable to the hitherto reported values for CMPs. [21] Solid-statediffuse-reflectanceUV/vis measurements show ar ange of discernibleadsorptione dges starting at 470nmfor SNP-BTT2 to 600nmfor SNP-BT1 (Figure2a).According to theKubelka-Munkequationthese values correspond to direct opticalbandgapsbetween 2.07 and2 .60eVand indirect band gaps between1 .71a nd 2.38 eV (FigureS30 in theS upporting Information).Asageneraltrend,polymers that containanaryl spacer also have al arger opticalb andg ap compared to their directly coupleda nalogues,e xceptf or then apthodithiophene (NDT)-based network(Ta ble1). Theseresults seem to contradict theoreticalpredictions that strong D-Ainteractionswould wident he band gap, [13a] andt hey highlightt he continuous problems of DFTw ithr espect to complex, organicD -A systems.…”

“…[15] Elemental composition was determined by combustion elemental analysis (EA), inductively coupled plasma-optical emission spectrometry (ICP-OES), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) under air and matched the expected values (Tables S3, S4, and S7-S14, Figures S2 and S43-S50, in the Supporting Information). [21] Solid-statediffuse-reflectanceUV/vis measurements show ar ange of discernibleadsorptione dges starting at 470nmfor SNP-BTT2 to 600nmfor SNP-BT1 (Figure2a).According to theKubelka-Munkequationthese values correspond to direct opticalbandgapsbetween 2.07 and2 .60eVand indirect band gaps between1 .71a nd 2.38 eV (FigureS30 in theS upporting Information).Asageneraltrend,polymers that containanaryl spacer also have al arger opticalb andg ap compared to their directly coupleda nalogues,e xceptf or then apthodithiophene (NDT)-based network(Ta ble1). Additional unreacted end groups show Cl and Br (0-3.26 wt %) along with Sn (0-0.85 wt %) in non-stoichiometric amounts.…”

Direct arylation polymerization toward efficient synthesis of benzo[1,2‐c:4,5‐c'] dithiophene‐4,8‐dione based donor‐acceptor alternating copolymers for organic optoelectronic applications

“…We carried out a preliminary optimization for the direct arylation of BDTD with CH active donors by testing two direct arylation conditions using Pd 2 (dba) 3 and Hermann's catalyst, respectively, in the synthesis of P1 and P2 (Table ). Both these conditions have been previously optimized for the C‐H activation of thiophene‐flanked monomers and have been used for synthesizing a variety of linear and 2D/3D conjugated networks. P1 was obtained in relatively low yields from both conditions since majority of products were obtained as oligomers in the hexane fraction (Supporting Information Fig.…”