Tracking the dynamics of ultrafast hole injection into copper thiocyanate (CuSCN) at the interface can be experimentally challenging. These challenges include restrictions in accessing the ultraviolet spectral range through transient electronic spectroscopy, where the absorption spectrum of CuSCN is located. Time-resolved vibrational spectroscopy solves this problem by tracking marker modes at specific frequencies and allowing direct access to dynamical information at the molecular level at donor-acceptor interfaces in real time. This study uses photoabsorber PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)-benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione))]) as a model system to explore and decipher the hole transfer dynamics of CuSCN using femtosecond (fs) mid-infrared (IR) spectroscopy. The time-resolved results indicate that excited PM6 exhibits a sharp vibrational mode at 1599 cm-1 attributed to the carbonyl group, matching the predicted frequency position obtained from time-dependent density functional theory (DFT) calculations. The fs mid-IR spectroscopy demonstrates a fast formation (<168 fs) and blue spectral shift of the CN stretching vibration from 2118 cm-1 for CuSCN alone to 2180 cm-1 for PM6/CuSCN, confirming the hole transfer from PM6 to CuSCN. The short interfacial distance and high frontier orbital delocalization obtained from the interfacial DFT models support a coherent and ultrafast regime for hole transfer. These results provide direct evidence for hole injection at the interface of CuSCN for the first time using femtosecond mid-IR spectroscopy and serve as a new investigative approach for interfacial chemistry and solar cell communities.
Intermolecular charge transfer (CT) complexes have emerged as versatile platforms with customizable optical properties that play a pivotal role in achieving tunable photoresponsive materials. In this study, we introduce an innovative approach for enhancing the modulation bandwidth and net data rates in optical wireless communications (OWCs) by manipulating combinations of monomeric molecules within intermolecular CT complexes. Concurrently, we extensively investigate the intermolecular charge transfer mechanism through diverse steady-state and ultrafast time-resolved spectral techniques in the mid-infrared range complemented by theoretical calculations using density functional theory. These intermolecular CT complexes empower precise control over the -3 dB bandwidth and net data rates in OWC applications. The resulting color converters exhibit promising performance, achieving a net data rate of â¼100 Mb/s, outperforming conventional materials commonly used in the manufacture of OWC devices. This research underscores the substantial potential of engineering intermolecular charge transfer complexes as an ongoing progression and commercialization within the OWC. This carries profound implications for future initiatives in high-speed and secure data transmission, paving the way for promising endeavors in this area.
We utilized a metal propionate solution to prepare polycrystalline bismuth-substituted yttrium iron garnets through the metal-organic decomposition process. After conducting thorough optimization, we successfully synthesized a garnet that exhibited a high magneto-optic response directly at the end of an optical fiber. A notable achievement of our work lies in the ability to restrict the size and position of the garnet to match the dimensions of the fiber's core. The functionalized fiber was integrated into a magneto-optical sensor setup, offering the flexibility to operate either in the Faraday rotation or magnetic circular dichroism mode.
One of the most effective approaches to optimizing the performance of perovskite solar cells is to fully understand the ultrafast carrier dynamics at the interfaces between absorber and transporting layers at both the molecular and atomic levels. Here, the injection dynamics of hot and relaxed charge carriers at the interface between the hybrid perovskite, formamidinium lead bromide (FAPbBr3), and the organic electron acceptor, IEICO-4F, are investigated and deciphered by using femtosecond (fs) mid-infrared (IR), transient absorption (TA), and fluorescence spectroscopies. The visible femtosecond-TA measurements reveal the generation of hot carriers and their transition to free carriers in the pure FAPbBr3 film. Meanwhile, the efficient extraction of hot carriers in the mixed FAPbBr3/IEICO-4F film is clearly evidenced by the complete disappearance of their spectral signature. More specifically, the time-resolved results reveal that hot carriers are injected from FAPbBr3 to IEICO-4F within 150 fs, while the transfer time for the relaxed carriers is about 205 fs. The time-resolved mid-IR experiments also demonstrate the ultrafast formation of two peaks at 2115 and 2233 cm-1, which can be attributed to the C≡N symmetrical and asymmetrical vibrational modes of anionic IEICO-4F, thus providing crystal clear evidence for the electron transfer process between the donor and acceptor units. Moreover, photoluminescence (PL) lifetime measurements reveal an approximately 10-fold decrease in the donor lifetime in the presence of IEICO-4F, thereby confirming the efficient electron injection from the perovskite to the acceptor unit. In addition, the efficient electron injection at the FAPbBr3/IEICO-4F interface and its impact on the C≡N bond character are experimentally evidenced and align with density functional theory (DFT) calculations. This work offers new insights into the electron injection process at the FAPbBr3/IEICO-4F interface, which is crucial for developing efficient optoelectronic devices.
Heterogeneous photocatalysis is considered as an ecofriendly and sustainable approach for addressing energy and environmental persisting issues. Recently, heterogeneous photocatalysts based on covalent organic frameworks (COFs) have gained considerable attention due to their remarkable performance and recyclability in photocatalytic organic transformations, offering a prospective alternative to homogeneous photocatalysts based on precious metal/organic dyes. Herein, we report Hex-Aza-COF-3 as a metal-free, visible-light-activated, and reusable heterogeneous photocatalyst for the synthesis of 2,3-dihydrobenzofurans, as a pharmaceutically relevant structural motif, via the selective oxidative [3+2] cycloaddition of phenols with olefins. Moreover, we demonstrate the synthesis of natural products (±)-conocarpan and (±)-pterocarpin via the [3+2] cycloaddition reaction as an important step using Hex-Aza-COF-3 as a heterogeneous photocatalyst. Interestingly, the presence of phenazine and hexaazatriphenylene as rigid heterocyclic units in Hex-Aza-COF-3 strengthens the covalent linkages, enhances the absorption in the visible region, and narrows the energy band, leading to excellent activity, charge transport, stability, and recyclability in photocatalytic reactions, as evident from theoretical calculations and real-time information on ultrafast spectroscopic measurements.
Structural modifications to molecular systems that lead to the control of photon emission processes at the interfaces between photoactive materials play a key role in the development of fluorescence sensors, X-ray imaging scintillators, and organic light-emitting diodes (OLEDs). In this work, two donor-acceptor systems were used to explore and reveal the effects of slight changes in chemical structure on interfacial excited-state transfer processes. A thermally activated delayed fluorescence (TADF) molecule was chosen as the molecular acceptor. Meanwhile, two benzoselenadiazole-core MOF linker precursors, Ac-SDZ and SDZ, with the presence and absence of a C≡C bridge, respectively, were carefully chosen as energy and/or electron-donor moieties. We found that the SDZ -TADF donor-acceptor system exhibited efficient energy transfer, as evidenced by steady-state and time-resolved laser spectroscopy. Furthermore, our results demonstrated that the Ac-SDZ-TADF system exhibited both interfacial energy and electron transfer processes. Femtosecond-mid-IR (fs-mid-IR) transient absorption measurements revealed that the electron transfer process takes place on the picosecond timescale. Time-dependent density functional theory (TD-DFT) calculations confirmed that photoinduced electron transfer occurred in this system and demonstrated that it takes place from C≡C in Ac-SDZ to the central unit of the TADF molecule. This work provides a straightforward way to modulate and tune excited-state energy/charge transfer processes at donor-acceptor interfaces.
Mixed-matrix membranes (MMMs) based on luminescent metal-organic frameworks (MOFs) and emissive polymers with the combination of their unique advantages have great potential in separation science, sensing, and light-harvesting applications. Here, we demonstrate MMMs for the field of high-speed visible-light communication (VLC) using a very efficient energy transfer strategy at the interface between a MOF and an emissive polymer. Our steady-state and ultrafast time-resolved experiments, supported by high-level density functional theory calculations, revealed that efficient and ultrafast energy transfer from the luminescent MOF to the luminescent polymer can be achieved. The resultant MMMs exhibited an excellent modulation bandwidth of around 80 MHz, which is higher than those of most well-established color-converting phosphors commonly used for optical wireless communication. Interestingly, we found that the efficient energy transfer further improved the light communication data rate from 132 Mb/s of the pure polymer to 215 Mb/s of MMMs. This finding not only showcases the promise of the MMMs for high-speed VLC but also highlights the importance of an efficient and ultrafast energy transfer strategy for the advancement of data rates of optical wireless communication.
Aggregation-induced emission enhancement (AIEE) is a process recently exploited in solid-state materials and organic luminophores, and it is explained by tight-molecular packaging. However, solution-phase AIEE and its formation mechanism have not been widely explored. This work investigated AIEE phenomena in two donor-acceptor-donor-type benzodiazole-based molecules (the organic building block in metal-organic frameworks) with an acetylene and phenyl π-conjugated backbone tapered with a carboxylic acid group at either end. This was done using time-resolved electronic and vibrational spectroscopy in conjunction with time-dependent density functional theory (TD-DFT) calculations. Fluorescence up-conversion spectroscopy and time-correlated single-photon counting conclusively showed an intramolecular charge transfer-driven aggregate emission enhancement. This is shown by a red spectral shift of the emission spectra as well as an increase in the fluorescence lifetime from 746 ps at 1.0 × 10-11 to 2.48 ns at 2.0 × 10-3 M. The TD-DFT calculations showed that a restricted intramolecular rotation mechanism is responsible for the enhanced emission. The femtosecond infrared (IR) transient absorption results directly revealed the structural dynamics of aggregate formation, as evident from the evolution of the C≡C vibrational marker mode of the acetylene unit upon photoexcitation. Moreover, the IR data clearly indicated that the aggregation process occurred over a time scale of 10 ps, which is consistent with the fluorescence up-conversion results. Interestingly, time-resolved results and DFT calculations clearly demonstrated that both acetylene bonds and the sulfur atom are the key requirements to achieve such a controllable aggregation-induced fluorescence enhancement. The finding of the work not only shows how slight changes in the chemical structure of fluorescent chromophores could make a tremendous change in their optical behavior but also prompts a surge of research into a profound understanding of the mechanistic origins of this phenomenon. This may lead to the discovery of new chemical strategies that aim to synthesize novel chromophores with excellent optical properties for light-harvesting applications.
Metal-Organic Frameworks , Thiadiazoles , Fluorescent Dyes , Spectrometry, Fluorescence
