Publication database

The generation, control and transfer of triplet excitons in molecular and hybrid systems is of great interest owing to their long lifetime and diffusion length in both solid-state and solution phase systems, and to their applications in light emission1, optoelectronics, photon frequency conversion and photocatalysis. Molecular triplet excitons (bound electron–hole pairs) are ‘dark states’ because of the forbidden nature of the direct optical transition between the spin-zero ground state and the spin-one triplet levels. Hence, triplet dynamics are conventionally controlled through heavy-metal-based spin–orbit coupling or tuning of the singlet–triplet energy splitting via molecular design. Both these methods place constraints on the range of properties that can be modified and the molecular structures that can be used. Here we demonstrate that it is possible to control triplet dynamics by coupling organic molecules to lanthanide-doped inorganic insulating nanoparticles. This allows the classically forbidden transitions from the ground-state singlet to excited-state triplets to gain oscillator strength, enabling triplets to be directly generated on molecules via photon absorption. Photogenerated singlet excitons can be converted to triplet excitons on sub-10-picosecond timescales with unity efficiency by intersystem crossing. Triplet exciton states of the molecules can undergo energy transfer to the lanthanide ions with unity efficiency, which allows us to achieve luminescent harvesting of the dark triplet excitons. Furthermore, we demonstrate that the triplet excitons generated in the lanthanide nanoparticle–molecule hybrid systems by near-infrared photoexcitation can undergo efficient upconversion via a lanthanide–triplet excitation fusion process: this process enables endothermic upconversion and allows efficient upconversion from near-infrared to visible frequencies in the solid state. These results provide a new way to control triplet excitons, which is essential for many fields of optoelectronic and biomedical research.

As the development of oxygen evolution co-catalysts (OECs) is being actively undertaken, the tailored integration of those OECs with photoanodes is expected to be a plausible avenue for achieving highly efficient solar-assisted water splitting. Here, we demonstrate that a black phosphorene (BP) layer, inserted between the OEC and BiVO₄ can improve the photoelectrochemical performance of pre-optimized OEC/BiVO₄ (OEC: NiOOH, MnO_x, and CoOOH) systems by 1.2∼1.6-fold, while the OEC overlayer, in turn, can suppress BP self-oxidation to achieve a high durability. A photocurrent density of 4.48 mA·cm⁻² at 1.23 V vs reversible hydrogen electrode (RHE) is achieved by the NiOOH/BP/BiVO₄ photoanode. It is found that the intrinsic p-type BP can boost hole extraction from BiVO₄ and prolong holes trapping lifetime on BiVO₄ surface. This work sheds light on the design of BP-based devices for application in solar to fuel conversion, and also suggests a promising nexus between semiconductor and electrocatalyst.

We investigate the photodissociation of helium-solvated cesium dimer cations using action spectroscopy and quantum chemical calculations. The spectrum of Cs₂He⁺ shows three distinct absorption bands into both bound and dissociative states. Upon solvation with further helium atoms, considerable shifts of the absorption bands are observed, exceeding 0.1 eV (850 cm⁻¹) already for Cs₂He₁₀⁺, along with significant broadening. The shifts are highly sensitive to the character of the excited state. Our calculations show that helium atoms adsorb on the ends of Cs₂⁺. The shifts are particularly pronounced if the excited state orbitals extend to the area occupied by the helium atoms. In this case, Pauli repulsion leads to a deformation of the excited state orbitals, resulting in the observed blue shift of the transition. Since the position of the weakly bound helium atoms is ill defined, Pauli repulsion also explains the broadening.

Multimodal imaging with photoacoustic microscopy (PAM) and optical coherence tomography (OCT) can be an effective method to evaluate the choroidal and retinal microvasculature. To improve the efficiency for visualizing capillaries, colloidal gold nanoparticles (AuNPs) have been applied as a multimodal contrast agent for both OCT and PAM imaging by taking advantage of the strong optical scattering and the strong optical absorption of AuNPs due to their surface plasmon resonance. Ultra-pure AuNPs were fabricated by femtosecond laser ablation, capped with polyethylene glycol (PEG), and administered to 13 New Zealand white rabbits and 3 Dutch Belted pigmented rabbits. The synthesized PEG-AuNPs (20.0 ± 1.5 nm) were demonstrated to be excellent contrast agents for PAM and OCT, and do not demonstrate cytotoxicity to bovine retinal endothelial cells in cell studies. The image signal from the retinal and choroidal vessels in living rabbits was enhanced by up to 82% for PAM and up to 45% for OCT, respectively, by the administered PEG-AuNPs, which enables detection of individual blood vessels by both imaging modalities. The biodistribution study demonstrated the AuNP accumulated primarily in the liver and spleen. Histology and TUNEL staining did not indicate cell injury or death in the lung, liver, kidney, spleen, heart, or eyes up to seven days after AuNP administration. PEG-AuNPs offer an efficient and safe contrast agent for multimodal ocular imaging to achieve improved characterization of microvasculature.

Hydrated singly charged magnesium ions [Mg(H₂O)_n]⁺ are thought to consist of an Mg²⁺ ion and a hydrated electron for n > 15. This idea is based on mass spectra, which exhibit a transition from [MgOH(H₂O)_n−1]⁺ to [Mg(H₂O)_n]⁺ around n = 15–22, black-body infrared radiative dissociation, and quantum chemical calculations. Here, we present photodissociation spectra of size-selected [Mg(H₂O)_n]⁺ in the range of n = 20–70 measured for photon energies of 1.0–5.0 eV. The spectra exhibit a broad absorption from 1.4 to 3.2 eV, with two local maxima around 1.7–1.8 eV and 2.1–2.5 eV, depending on cluster size. The spectra shift slowly from n = 20 to n = 50, but no significant change is observed for n = 50–70. Quantum chemical modeling of the spectra yields several candidates for the observed absorptions, including five- and six-fold coordinated Mg²⁺ with a hydrated electron in its immediate vicinity, as well as a solvent-separated Mg²⁺/e⁻ pair. The photochemical behavior resembles that of the hydrated electron, with barrierless interconversion into the ground state following the excitation.

Joint high-resolution multimodal photoacoustic microscopy (PAM) and optical coherence tomography (OCT) was developed to improve the efficiency for visualizing newly developed retinal neovascularization (RNV) and to monitor the dynamic changes of retinal vein occlusion (RVO) in living rabbits. The RNV and RVO models were created in New Zealand rabbits by Rose Bengal laser-induced RVO. Dual modalities imaging equipment, including color fundus photography, fluorescein angiography (FA), OCT, and PAM, was used to image and assess the changes of retinal vasculature. In vivo experimental results exhibited that not only the treatment boundaries and the position of the occluded vasculature but also the structure of individual RNV were markedly observed using PAM platform with great resolution and high image contrast. The laser light energy of 80 nJ was used to induce photoacoustic signal, which is approximately half the energy of the American National Standards Institute safety limit. A cross-sectional structure of RNV was identified with the OCT modality. Furthermore, vibrant transformations in the RNV and the retinal morphology were examined at different times after laser occlusion: days 4, 28, 35, 49, and 90. PAM revealed high contrast and high resolution vascular imaging of the retina and choroid with amplified penetration depth. Through the present custom-built imaging system, both RNV and RVO can be reconstructed and observed in two and three dimensions. A unique dual modality A unique dual modality PAM and OCT can help precisely visualize and distinguish individual microvessels, microvessel depth, and the surrounding anatomy. Thus, the proposed multimodal ocular imaging platform may offer a potential equipment to enhance classification of microvasculature in a reliable and proficient manner in larger rabbit eyes.

Mid-infrared (MIR) microscopy provides rich chemical and structural information about biological samples, without staining. Conventionally, the long MIR wavelength severely limits the lateral resolution owing to optical diffraction; moreover, the strong MIR absorption of water ubiquitous in fresh biological samples results in high background and low contrast. To overcome these limitations, we propose a method that employs photoacoustic detection highly localized with a pulsed ultraviolet laser on the basis of the Grüneisen relaxation effect. For cultured cells, our method achieves water-background suppressed MIR imaging of lipids and proteins at ultraviolet resolution, at least an order of magnitude finer than the MIR diffraction limits. Label-free histology using this method is also demonstrated in thick brain slices. Our approach provides convenient high-resolution and high-contrast MIR imaging, which can benefit the diagnosis of fresh biological samples.

Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, Iminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.

The functionality of organic semiconductor devices crucially depends on molecular energies, namely the ionisation energy and the electron affinity. Ionisation energy and electron affinity values of thin films are, however, sensitive to film morphology and composition, making their prediction challenging. In a combined experimental and simulation study on zinc-phthalocyanine and its fluorinated derivatives, we show that changes in ionisation energy as a function of molecular orientation in neat films or mixing ratio in blends are proportional to the molecular quadrupole component along the π-π-stacking direction. We apply these findings to organic solar cells and demonstrate how the electrostatic interactions can be tuned to optimise the energy of the charge-transfer state at the donor−acceptor interface and the dissociation barrier for free charge carrier generation. The confirmation of the correlation between interfacial energies and quadrupole moments for other materials indicates its relevance for small molecules and polymers.

Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO₂^.−(H₂O)_n is relevant for electrochemical carbon dioxide functionalization. CO₂^.−(H₂O)_n (n=2–61) is investigated by using infrared action spectroscopy in the 1150–2220 cm⁻¹ region in an ICR (ion cyclotron resonance) cell cooled to T=80 K. The spectra show an absorption band around 1280 cm⁻¹, which is assigned to the symmetric C−O stretching vibration ν_s. It blueshifts with increasing cluster size, reaching the bulk value, within the experimental linewidth, for n=20. The antisymmetric C−O vibration ν_as is strongly coupled with the water bending mode ν₂, causing a broad feature at approximately 1650 cm⁻¹. For larger clusters, an additional broad and weak band appears above 1900 cm⁻¹ similar to bulk water, which is assigned to a combination band of water bending and libration modes. Quantum chemical calculations provide insight into the interaction of CO₂^.− with the hydrogen-bonding network.