The Excited-State Lifetime of Poly(NDI2OD-T2) Is Intrinsically Short
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Bredas, Jean-Luc
Publications and source records attributed to Bredas, Jean-Luc.
Thermally conductive ultra-low-k dielectric layers based on two-dimensional covalent organic framewo
Explore the source record for details and available documents.
Evans, Austin M.↗
Electronically Coupled 2D Polymer/MoS 2 Heterostructures
Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS 2 heterostructures. In this work, control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS 2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Design and synthesis of two-dimensional covalent organic frameworks with four-arm cores: prediction of remarkable ambipolar charge-transport properties
Theoretical and experimental investigations of diacetylene-linked COFs with remarkable charge-transport properties.
Thomas, Simil↗
Pathway Complexity in the Stacking of Imine-Linked Macrocycles Related to Two-Dimensional Covalent Organic Frameworks
Interlayer interactions play an important role in the formation of two-dimensional covalent organic frameworks (2D COFs), yet the effects of monomer structure on COF formation, crystallinity, and susceptibility to exfoliation are not well understood. Here we probe these effects by studying the stacking behavior of imine-linked macrocycles that represent discrete models of 2D COFs. Specifically, macrocycles based on terephthaldehyde (PDA) or 2,5-dimethoxyterephthaldehyde (DMPDA) stack upon cooling molecularly dissolved solutions. Both macrocycles assemble cooperatively with similar Delta H-e values of -97 kJ/mol and -101 kJ/mol, respectively, although the DMPDA macrocycle assembly process showed a more straightforward temperature dependence. Density functional theory calculations of the stacking of PDA macrocycles suggested two stable configurations that were close in energy. Circular dichroism spectroscopy performed on macrocycles bearing chiral side chains revealed a helix reversion process for the PDA macrocycles that was not observed for the DMPDA macrocycles. Given the structural similarity of these monomers, these findings demonstrate that the stacking processes associated with nanotubes derived from these macrocycles, as well as for the corresponding COFs, are complex and susceptible to kinetic traps, casting doubt on the relevance of thermodynamic arguments for improving materials quality. Rather, a deeper understanding of the mechanism of supramolecular polymerization and its interplay with polymerization and error correction during COF synthesis is needed for improved control of the crystallinity and morphology of these emerging materials.
Wang, Shiwei↗
Intramolecular Noncovalent Interactions Facilitate Thermally Activated Delayed Fluorescence (TADF)
In the conventional molecular design of thermally activated delayed fluorescence (TADF) organic emitters, simultaneously achieving a fast rate of reverse intersystem crossing (RISC) from the triplet to the singlet manifold and a fast rate of radiative decay is a challenging task. A number of recent experimental data, however, point to TADF emitters with intramolecular π-π interactions as a potential pathway to overcome the issue. Here, we report a comprehensive investigation of TADF emitters with intramolecular π…π or lone-pair…π non-covalent interactions. We uncover the impact of those intramolecular non-covalent interactions on the TADF properties. In particular, we find that folded geometries in TADF molecules can trigger lone-pair…π interactions, introduce a n → π* character of the relevant transitions, enhance the singlet-triplet spin-orbit coupling, and ultimately greatly facilitate the RISC process. Furthermore, this work provides a robust foundation for the molecular design of a novel class of highly efficient TADF emitters in which intramolecular non-covalent interactions play a critical function.
36 MATERIALS SCIENCE↗
Every Atom Counts: Elucidating the Fundamental Impact of Structural Change in Conjugated Polymers for Organic Photovoltaics
As many conjugated polymer-based organic photovoltaic (OPV) materials provide substantial solar power conversion efficiencies (as high as 13%), it is important to develop a deeper understanding of how the primary repeat unit structures impact device performance. In this work, we have varied the group 14 atom (C, Si, Ge) at the center of a bithiophene fused ring to elucidate the impact of a minimal repeat unit structure change on the optical, transport, and morphological properties, which ultimately control device performance. Careful polymerization and polymer purification produced three “one-atom change” donor–acceptor conjugated alternating copolymers with similar molecular weights and dispersities. DFT calculation, absorption spectroscopy, and high-temperature solution 1 H nuclear magnetic resonance (NMR) results indicate that poly(dithienosilole-alt-thienopyrrolodione), P(DTS-TPD), and poly(dithienogermole-alt-thienopyrrolodione), P(DTG-TPD) exhibit different rotational conformations when compared to poly(cyclopentadithiophene-alt-thienopyrrolodione), P(DTC-TPD). Solid-state 1 H MAS NMR experiments reveal that the greater probability of the anticonformation in P(DTS-TPD) and P(DTG-TPD) prevail in the solid phase. The conformational variation seen in solution and solid-state NMR in turn affects the polymer stacking and intermolecular interaction. Two-dimension 1 H- 1 H DQ-SQ NMR correlation spectra shows aromatic–aromatic correlations for P(DTS-TPD) and P(DTG-TPD), which on the other hand is absent for P(DTC-TPD). In a thin-film interchain packing study using grazing incidence wide-angle X-ray scattering (GIWAXS), we observe the π-face of the conjugated backbones of P(DTC-TPD) aligned edge-on to the substrate, whereas in contrast the π-faces of P(DTS-TPD) and P(DTG-TPD) align parallel to the surface. These differences in polymer conformations and backbone orientations lead to variations in the OPV performance of blends with the fullerene PC 71 BM, with the device containing P(DTC-TPD):PCBM having a lower fill factor and a lower power conversion efficiency. Ultrafast transient absorption spectroscopy shows the P(DTC-TPD):PCBM blend to have a more pronounced triplet formation from bimolecular recombination of initially separated charges. With a combination of sub-bandgap external quantum efficiency measurements and DFT calculations, we present evidence that the greater charge recombination loss is the result of a lower lying triplet energy level for P(DTC-TPD), leading to a higher rate of recombination and lower OPV device performance. In conclusion, importantly, this study ties ultimate photovoltaic performance to morphological features in the active films that are induced from the processing solution and are a result of minimal one-atom differences in polymer repeat unit structure.
36 MATERIALS SCIENCE↗