Impact of Conjugated Polymer Characteristics on the Enrichment of Single-Chirality Single-Walled Carbon Nanotubes

Abstract

Polymer characteristics influence the chiral selectivity and yield in the enrichment of (7,6) from Signis SG76 in toluene by various fluorene homopolymers and copolymers. Fluorene homopolymers such as poly(9,9-di-n-dodecylfluorene) (PFDD) and copolymers with anthracene such as poly[(9,9dihexylfluorenyl-2,7-diyl)-co-(9,10-anthracene)] (PFH-A) result in high (7,6) selectivities of up to 67 and 72%, respectively. The selectivity is calculated by optical absorption using a known extinction coefficient and also evaluated by Raman scattering and photoluminescence excitation. In contrast, poly[(9,9-dioctyl-2,7divinylenefluorenylene)-alt-co-(9,10-anthracene)] (PFO=A), with a double-bond spacer, results in (9,5) dominant extractions with the purity of (9,5) up to 80% after ultracentrifugation, which is believed to be the first report on the successful enrichment of (9,5) by conjugated polymers. The chiral selectivity is also greatly impacted by the length of alkyl side chain of fluorene homopolymers: hexyl group has low selectivity, while octyl, dodecyl, and tetradecyl (PFTD) groups show high selectivity toward (7,6), and the octadecyl group is prone to include bigger tubes. Interestingly, a chiral selection transition from (7,6) to (8,6) occurred using PFTD after a few enrichment cycles. The chiral purity of (8,6) was greatly improved from 50 to 86% after slow filtration. Polymer molecular weight (MW, here PFDD) also plays a role in the selectivity and yield. Low MW leads to a low yield, and high MW leads to a low selectivity, with the optimal range (M n ) being ca. 20−35 kDa when the polydisperse index is ca. 2−3. Molecular dynamics simulation confirms that different lengths of side chain of polyfluorene have different wrapping stabilities toward specific chirality, where PFTD shows greater stability toward (8,6) than (7,6).

Broadband Full-Spectrum Raman Excitation Mapping Reveals Intricate Optoelectronic–Vibrational Resonance Structure of Chirality-Pure Single-Walled Carbon Nanotubes

“…The (7,5) and (6,5) species were purified with a polymer wrapping procedure carried out in toluene. 17,18 These were then deposited by filtration on polytetrafluoroethylene (PTFE) membranes, producing uniform, opaque films of about 1 cm 2 in area. Uniform films like these are ideal for FS-REM.…”

“…These samples were chosen because of their availability in purified form, common use within the SWCNT research community, and because they have optoelectronic resonances in the wavelength range of the illumination. The (7,5) and (6,5) species were purified with a polymer wrapping procedure carried out in toluene. , These were then deposited by filtration on polytetrafluoroethylene (PTFE) membranes, producing uniform, opaque films of about 1 cm 2 in area. Uniform films like these are ideal for FS-REM.…”

“…at an output of 30% and a duty cycle of 60% for 30 min, followed by centrifugation at 1310 rad/s (12500 rpm) for 60 min (SS-34 rotor, a relative centrifugal force of 18700 g , g ≡ 9.81 m/s 2 ). The enrichment was repeated for multiple cycles to maximize the mass yield . The enriched (6,5) and (7,5) were previously found to have an increasing number of defects as the total sonication time was increased.…”

“…The enrichment was repeated for multiple cycles to maximize the mass yield. 18 The enriched (6,5) and (7,5) were previously found to have an increasing number of defects as the total sonication time was increased.…”

Solvatochromism in SWCNTs suspended by conjugated polymers in organic solvents

“…36 Unraveling this puzzle is not simplified by the fact that, in the case of polymers, there is no standardized scheme for analyzing the strength of solvatochromism expressed as ΔE ii . In this regard, the authors define it commonly as: [21][22][23][24]33,36,67,68…”