[n]Cycloparaphenylenes behave as molecular templates of "perfectly chemically defined" single-wall carbon nanotubes. These [n]CPP molecules have electronic, mechanical, and chemical properties in size correspondence with their giant congeners. Under mechanical stress, they form charge-transfer salts, or complexes with fullerene, by one-electron concave-convex electron transfer.
As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress charge recombination. Here we investigate two series of in-chain donor-acceptor copolymers, PTPDnT and PBTInT, based on thieno[3,4-c]pyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers. Thiophene addition progressively raises polymer HOMOs but marginally affects their band gaps. FT-Raman spectra indicate that PTPDnT and PBTInT conjugation lengths scale with nT catenation up to n = 3 and then saturate for longer oligomer. Furthermore, the effects of oligothiophene alkylation position are explored, revealing that the alkylation pattern greatly affects film morphology and PSC performance. The 3T with "outward" alkylation in PTPD3T and PBTI3T affords optimal π-conjugation, close stacking, long-range order, and high hole mobilities (0.1 cm(2)/(V s)). These characteristics contribute to the exceptional ∼80% fill factors for PTPD3T-based PSCs with PCE = 7.7%. The results demonstrate that 3T is the optimal donor unit among nTs (n = 1-4) for photovoltaic polymers. Grazing incidence wide-angle X-ray scattering, transmission electron microscopy, and time-resolved microwave conductivity measurements reveal that the terthiophene-based PTPD3T blend maintains high crystallinity with appreciable local mobility and long charge carrier lifetime. These results provide fundamental materials structure-device performance correlations and suggest guidelines for designing oligothiophene-based polymers with optimal thiophene catenation and appropriate alkylation pattern to maximize PSC performance.
The vibrational Raman spectra of several series of aromatic and quinoidal compounds have been analyzed considering the downshifts and upshifts of the frequencies of the relevant Raman bands as a function of the number of repeating units. Oligothiophenes, oligophenylene-vinylenes, and oligoperylenes (oligophenyls) derivatives are studied in a common context. These shifts are taken as spectroscopic fingerprints of the changes in π-conjugation. For a given family, aromatic and quinoidal oligomers have been studied together, and according to their Raman frequency shifts located in the two-well BLA-energy curve of their ground electronic state as a function of the bond-length-alternation pattern (BLA). The connection among BLA values, π-conjugation, and Raman frequencies is taken here as the basis of the study. These Raman shifts/BLA changes have been related to important electronic properties of these one-dimensional linear π-electron delocalized systems such as quinoidal (polyene) and aromatic characters.
While the chemistry of open-shell singlet diradicaloids has been successfully developed in recent years, the synthesis of π-conjugated systems with poly-radical characters (i.e., beyond diradical) in the singlet ground state has been mostly unsuccessful. In this study, we report the synthesis and isolation of two fully fused macrocycles containing four (4MC) and six (6MC) alternatingly arranged quinoidal/aromatic carbazole units. Ab initio electronic structure calculations and various experimental measurements indicate that both 4MC and 6MC have an open-shell singlet ground state with moderate tetraradical and hexaradical characters, respectively. Both compounds can be thermally populated to high-spin excited states, resulting in weak magnetization at room temperature. Our study represents the first demonstration of singlet π-conjugated molecules with poly-radical characters and also gives some insights into molecular magnetism in neutral π-conjugated polycyclic heteroarenes.
Titanium
dental implants are a multibillion dollar market in the
United States alone. The growth of a bacterial biofilm on a dental
implant can cause gingivitis, implant loss, and expensive subsequent
care. Herein, we demonstrate the efficient eradication of dental biofilm
on titanium dental implants via swarming magnetic microrobots based
on ferromagnetic (Fe3O4) and photoactive (BiVO4) materials through polyethylenimine micelles. The ferromagnetic
component serves as a propulsion force using a transversal rotating
magnetic field while BiVO4 is the photoactive generator
of reactive oxygen species to eradicate the biofilm colonies. Such
photoactive magnetically powered, precisely navigated microrobots
are able to destroy biofilm colonies on titanium implants, demonstrating
their use in precision medicine.
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