Bright State Sensitized Triplet Energy Transfer from Quantum Dot to Molecular Acceptor Revealed by Temperature Dependent Energy Transfer Dynamics.

Quantum dot (QD) sensitized molecular triplet excited state generation has been a promising alternative for traditional triplet state harvesting schemes. However, the correlation between QD bright/dark states and QD sensitized triplet energy transfer (TET) has been unclear. Herein, we studied the bright/dark states contribution to TET with CdSe/CdS core/shell QD-oligothiophene as the model system. Equilibrium between QD bright and dark states was tuned by changing temperature, and TET dynamics were monitored with transient absorption spectroscopy. Analysis of acceptor triplet excited state growth kinetics yields rates of TET from bright and dark states as 0.492 ± 0.011 ns-1 and 0.0271 ± 0.0014 ns-1 at 5 K, suggesting significant contribution of bright states to TET. The result was rationalized by bright state wave function components with the same electron/hole spin projections leading to nonzero TET probability. The study provides new insights into QD sensitized TET mechanisms and inspiration for future TET efficiency optimization through QD exciton engineering.

High-Strength, Microporous, Two-Dimensional Polymer Thin Films with Rigid Benzoxazole Linkage.

Two-dimensional (2D) rigid polymers provide an opportunity to translate the high-strength, high-modulus mechanical performance of classic rigid-rod 1D polymers across a plane by extending covalent bonding into two dimensions while simultaneously reducing density due to microporosity by structural design. Thus far, this potential has remained elusive because of the challenge of producing high-quality 2D polymer thin films, particularly those with irreversible, rigid benzazole linkages. Here, we present a facile two-step process that allows the deposition of a uniform intermediate film network via reversible, non-covalent interactions, followed by a subsequent solid-state annealing step that facilitates the irreversible conversion to a 2D covalently bonded polymer product with benzoxazole linkages. We demonstrate the versatility of this synthesis method by producing films with four different aromatic core units. The resulting films show microporosity and anisotropy with a 2D layered structure that can be exfoliated into few-layer nanosheets using a freeze-thaw method. These films have promising mechanical properties with an in-plane ultimate tensile strength of nearly 40 MPa and axial tensile and transverse compressive elastic moduli on the scale of several GPa, rivaling the performance of solution-cast films of 1D polybenzoxazole, as well as several other 1D high-strength polymer films.

Enhancing the efficiency of semiconducting quantum dot photocatalyzed atom transfer radical polymerization by ligand shell engineering.

Manipulating the ligand shell of semiconducting quantum dots (QDs) has proven to be a promising strategy to enhance their photocatalytic performance for small molecule transformations, such as H2 evolution and CO2 reduction. However, ligand-controlled catalysis for macromolecules, which differ from small molecules in penetrability and charge transfer behavior due to their bulky sizes, still remains undiscovered. Here, we systematically investigate the role of surface ligands in the photocatalytic performance of cadmium selenide (CdSe) QDs in light-induced atom transfer radical polymerization (ATRP) by using thiol-based ligands with various polarities and chain lengths. A highly enhanced polymerization efficiency was observed when 3-mercapto propionic acid (MPA), a short-chain and polar ligand, was used to modify the CdSe QDs' surface, achieving high chain-end fidelity, good temporal control, and a dispersity of 1.18, while also tolerating a wide-range of functional monomers ranging from acrylates to methacrylates and fluorinated monomers. Transient absorption spectroscopy and time-resolved photoluminescence studies reveal interesting mechanistic details of electron and hole transfers from the excited QDs to the initiators and 3-MPA capping ligands, respectively, providing key mechanistic insight of these ligand controlled and QD photocatalyzed ATRP processes. The thiolate ligands were found to serve as an efficient hole acceptor for QDs, which facilitates the formation of a charge-separated state, followed by electron transfer from the conduction band edge to initiators and ultimately suppressing charge recombination within the QD.

Light-Mediated Polymerization Induced by Semiconducting Nanomaterials: State-of-the-Art and Future Perspectives.

Direct capture of solar energy for chemical transformation via photocatalysis proves to be a cost-effective and energy-saving approach to construct organic compounds. With the recent growth in photosynthesis, photopolymerization has been established as a robust strategy for the production of specialty polymers with complex structures, precise molecular weight, and narrow dispersity. A key challenge in photopolymerization is the scarcity of effective photomediators (photoinitiators, photocatalysts, etc.) that can provide polymerization with high yield and well-defined polymer products. Current efforts on developing photomediators have mainly focused on organic dyes and metal complexes. On the other hand, nanomaterials (NMs), particularly semiconducting nanomaterials (SNMs), are suitable candidates for photochemical reactions due to their unique optical and electrical properties, such as high absorption coefficients, large charge diffusion lengths, and broad absorption spectra. This review provides a comprehensive insight into SNMs' photomediated polymerizations and highlights the roles SNMs play in photopolymerizations, types of polymerizations, applications in producing advanced materials, and the future directions.

Enhanced intersystem crossing of boron dipyrromethene by TEMPO radical.

Radical enhanced intersystem crossing (EISC) of organic chromophores is an important approach to generate a long-lived triplet state for various electronic and optoelectronic applications. However, structural factors and design rules to promote EISC are not entirely clear. In this work, we report a series of boron dipyrromethene (BODIPY) derivatives covalently linked with a 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical with varying distances and topologies. We show that the incorporation of the TEMPO radical to BODIPY results in strong fluorescence quenching by up to 85% as a result of EISC and enhanced internal conversion. In BDP-2AR [2-(4-methyleneamino-TEMPO) BODIPY], a dyad with the shortest BODIPY-TEMPO through-bond distance, we observe the fastest EISC rate (τisc = 1.4 ns) and the longest triplet excited state lifetime (τT = 32 µs) compared to other distance and geometry variations. Contrary to previous reports and a general presumption, the BODIPY-TEMPO through-bond distance in this system does not play a significant role on the triplet formation rate and yield. Density functional theory suggests a folding of the TEMPO radical to form a sandwich-like structure with a BODIPY ring that leads to a decrease in the through-space distance, providing a new and an interesting insight for the radical enhanced intersystem.

Competition of Dexter, Förster, and charge transfer pathways for quantum dot sensitized triplet generation.

Quantum dot (QD) sensitized triplet exciton generation has demonstrated promising applications in various fields such as photon up-conversion through triplet-triplet annihilation. However, how direct triplet energy transfer from the QD to the acceptor through Dexter energy transfer (DET) competes with other processes, including Förster resonance energy transfer (FRET) and charge transfer, remains poorly understood. Herein, the competition of these pathways for QD-sensitized triplet excited state generation in CdSe QD-modified boron dipyrromethene (BODIPY) complexes is studied using transient absorption spectroscopy. After excitation of the CdSe QD with 500 nm pulses, the BODIPY triplet excited state is generated through charge recombination in a charge separated intermediate state (QD-·-BODIPY+·). This intermediate state is populated either through FRET from the excited QD to BODIPY followed by electron transfer from the singlet excited state of BODIPY to the QD or through hole transfer from the excited QD to BODIPY. The triplet excited state generation efficiencies from the FRET and hole transfer pathways are estimated to be (6.18 ± 1.39)% and (13.5 ± 3.1)%, respectively. Compared to these indirect pathways, direct DET from the QD to the BODIPY triplet state is kinetically not competitive. These results demonstrate that sequential charge transfer can be an efficient pathway for triplet excited state generation in QD-acceptor complexes.

Lead Halide Perovskite Nanocrystals as Photocatalysts for PET-RAFT Polymerization under Visible and Near-Infrared Irradiation.

A key challenge of harvesting solar energy for chemical transformations is the scarcity of photocatalysts with broad activation wavelength and easily tunable band structures. Here, we introduce lead halide perovskite (CsPbBr3) nanocrystals as band-edge-tunable photocatalysts for efficient photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. PET-RAFT polymerization of various functional monomers is successfully conducted using a broad range of irradiation sources ranging from blue to red light (460 to 635 nm), resulting in polymer products with narrow dispersity (D = 1.02-1.13) and high degree of chain-end fidelity. Furthermore, the giant two-photon absorption cross-section of CsPbBr3 enables activation with a light source in the near-infrared region (laser pulses centered at 800 nm) for the PET-RAFT process.

Direct triplet sensitization of oligothiophene by quantum dots.

Effective sensitization of triplet states is essential to many applications, including triplet-triplet annihilation based photon upconversion schemes. This work demonstrates successful triplet sensitization of a CdSe quantum dot (QD)-bound oligothiophene carboxylic acid (T6). Transient absorption spectroscopy provides direct evidence of Dexter-type triplet energy transfer from the QD to the acceptor without populating the singlet excited state or charge transfer intermediates. Analysis of T6 concentration dependent triplet formation kinetics shows that the intrinsic triplet energy transfer rate in 1 : 1 QD-T6 complexes is 0.077 ns-1 and the apparent transfer rate and efficiency can be improved by increasing the acceptor binding strength. This work demonstrates a new class of triplet acceptor molecules for QD-based upconversion systems that are more stable and tunable than the extensively studied polyacenes.

Enhanced triplet state generation through radical pair intermediates in BODIPY-quantum dot complexes.

Generation of triplet excited states through radical pair intermediates has been extensively studied in molecular complexes. Similar schemes remain rare in hybrid structures of quantum dot-organic molecules, despite intense recent interest of quantum dot sensitized triplet excited state generation. Herein, we demonstrate that the efficiency of the intersystem crossing from the singlet to the triplet state in boron dipyrromethene (BODIPY) can be enhanced in CdSe quantum dot-BODIPY complexes through a radical pair intermediate state consisting of an unpaired electron in the quantum dot conduction band and that in oxidized BODIPY. By transient absorption spectroscopy, we show that the excitation of BODIPY with 650 nm light leads to the formation of a charge separated state by electron transfer from BODIPY to CdSe (with a time constant of 6.33 ± 1.13 ns), competing with internal conversion to the ground state within BODIPY, and the radical pair state decays subsequently by back charge recombination to generate a triplet excited state (with a time constant of 158 ± 28 ns) or the ground state of BODIPY. The overall quantum efficiency of BODIPY triplet excited state generation was determined to be (27.2 ± 3.0)%. The findings of efficient triplet state formation and intermediate radical pair states in this hybrid system suggest that quantum dot-molecule complexes may be a promising platform for spintronics applications.

Semiconductor Quantum Dots as Photocatalysts for Controlled Light-Mediated Radical Polymerization.

Light-mediated radical polymerization has benefited from the rapid development of photoredox catalysts and offers many exceptional advantages over traditional thermal polymerizations. Nevertheless, the majority of the work relies on molecular photoredox catalysts or expensive transition metals. We exploited the capability of semiconductor quantum dots (QD) as a new type of catalyst for the radical polymerization that can harness natural sunlight. Polymerizations of (meth)acrylates, styrene, and construction of block copolymers were demonstrated, together with temporal control of the polymerization by the light source. Photoluminescence experiments revealed that the reduction of alkyl bromide initiator by photoexcited QD is the key to this light-mediated radical polymerization.

Macroscopic Alignment of One-Dimensional Conjugated Polymer Nanocrystallites for High-Mobility Organic Field-Effect Transistors.

Controlling the morphology of polymer semiconductors remains a fundamental challenge that hinders their widespread applications in electronic and optoelectronic devices and commercial feasibility. Although conjugated polymer nanowires (NWs) are envisioned to afford high charge-carrier mobility, the alignment of preformed conjugated polymer NWs has not been reported. Here, we demonstrate an extremely simple and effective strategy to generate well-aligned arrays of one-dimensional (1D) polymer semiconductors that exhibit remarkable enhancement in charge transport using a solution shear-coating technique. We show that solution shear coating of poly(alkylthiophene) NWs induces extension or coplanarization of the polymer backbone and highly aligned network films, which results in enhanced intra- and intermolecular ordering and reduced grain boundaries. Consequently, highly aligned poly(3-hexylthiophene) NWs exhibited over 33-fold enhancement in the average carrier mobility, with the highest mobility of 0.32 cm(2) V(-1) s(-1) compared to pristine films. The presented platform is a promising strategy and general approach for achieving well-aligned 1D nanostructures of polymer semiconductors and could enable the next generation of high-performance flexible electronic devices for a wide range of applications.