Conformation-Driven Responsive 1D and 2D Lanthanide-Metal-Organic Framework Heterostructures for High-Security Photonic Barcodes.

Development of luminescent segmented heterostructures featuring multiple spatial-responsive blocks is important to achieve miniaturized photonic barcodes toward anti-counterfeit applications. Unfortunately, dynamic manipulation of the spatial color at micro/nanoscale still remains a formidable challenge. Here, a straightforward strategy is proposed to construct spatially varied heterostructures through amplifying the conformation-driven response in flexible lanthanide-metal-organic frameworks (Ln-MOFs), where the thermally induced minor conformational changes in organic donors dramatically modulate the photoluminescence of Ln acceptors. Notably, compositionally and structurally distinct heterostructures (1D and 2D) are further constructed through epitaxial growth of multiple responsive MOF blocks benefiting from the isomorphous Ln-MOF structures. The thermally controlled emissive colors with distinguishable spectra carry the fingerprint information of a specific heterostructure, thus allowing for the effective construction of smart photonic barcodes with spatially responsive characteristics. The results will deepen the understanding of the conformation-driven responsive mechanism and also provide guidance to fabricate complex stimuli-responsive hierarchical microstructures for advanced optical recording and high-security labels.

Isomerization of surface functionalized SWCNTs and the critical influence on photoluminescence: static calculations and excited-state dynamics simulations.

Single-walled carbon nanotubes (SWCNTs) functionalized with sparse surface chemical groups are promising for a variety of optical applications such as quantum information and bio-imaging. However, the luminescence efficiencies and stability, two key aspects, undoubtedly govern their practical usage. Herein, we assess the surface migration of oxygen and triazine groups on as-modified SWCNT fragments by adopting transition state theory and explore the de-excitation of oxygen-functionalized SWCNT fragments by performing non-adiabatic excited-state dynamics simulations. According to the predicted moderate or even small reaction barriers, the migration of both oxygen and triazine groups is feasible from an sp3 defect configuration forming an energetically more stable sp2 configuration at moderate or even room temperatures. Such isomerization leads to drastically different light emission capabilities as indicated by the large or zero oscillator strengths. During the dynamics simulations, the lowest excited singlet (S1) state rapidly decays in energy within 20 fs and then fluctuates until the end, providing insights into the emission mechanism of SWCNTs. This study highlights the potential intrinsic limitations of surface-functionalized SWCNTs for luminescence applications.

Spatially Resolved Organic Whispering-Gallery-Mode Hetero-Microrings for High-Security Photonic Barcodes.

Whispering-gallery-mode (WGM) microcavities featuring distinguishable sharp peaks in a broadband exhibit enormous advantages in the field of miniaturized photonic barcodes. However, such kind of barcodes developed hitherto are primarily based on microcavities wherein multiple gain medias were blended into a single matrix, thus resulting in the limited and indistinguishable coding elements. Here, a surface tension assisted heterogeneous assembly strategy is proposed to construct the spatially resolved WGM hetero-microrings with multiple spatial colors along its circular direction. Through precisely regulating the charge-transfer (CT) strength, full-color microrings covering the entire visible range were effectively acquired, which exhibit a series of sharp and recognizable peaks and allow for the effective construction of high-quality photonic barcodes. Notably, the spatially resolved WGM hetero-microrings with multiple coding elements were finally acquired through heterogeneous nucleation and growth controlled by the directional diffusion between the hetero-emulsion droplets, thus remarkably promoting the security strength and coding capacity of the barcodes. The results would be useful to fabricate new types of organic hierarchical hybrid WGM heterostructures for optical information recording and security labels.

Steric Hindrance Governs the Photoinduced Structural Planarization of Cycloparaphenylene Materials.

Cycloparaphenylenes ([n]CPPs) and their derivatives are known for the unique size-dependent photophysical properties, which are largely attributed to the structural planarization-associated exciton localization, attracting substantial research attention. In this work, we show that the steric hindrance between neighboring structural units plays a key role in governing the photoinduced global/local structural planarization and electron-hole distribution features of [n]CPP materials, due to the tunable strength of H···H repulsion between neighboring units via structural modification or C-H distance variation as revealed by density functional theory (DFT) and time-dependent DFT calculations. According to our results, steric hindrance controls the manner and also the extent of excited-state structural planarization, where a weak (strong) steric hindrance favors (hinders) structural planarization upon relaxation in the first excited singlet (S1) state as compared to the ground (S0)-state structure. Depending on the molecular structures, steric hindrance leads to fully delocalized, partially separated, or more localized electron-hole distributions. For example, via H···H repulsion release by manually shortening the C-H distance or by chemical substitution of C-H with N atoms, the modified [10]CPP structures show fully planarized configurations (each dihedral angle can be less than 2°) and entirely delocalized electron-hole distribution upon photorelaxation. This work provides insights into the structural origin of the unusual photophysical properties of [n]CPPs and shows the promise of steric hindrance tuning in accessing diverse excited-state features in [n]CPP materials.

Revealing and Tuning the Photophysics of C=N Containing Photothermal Molecules: Excited State Dynamics Simulations.

Molecular photothermal conversion materials are recently attracting increasing attention for phototherapy applications. Herein we investigate the excitation and de-excitation processes of a photothermal molecule (C1TI) that is among the recently developed class of small-molecule-based photothermal imines with superb photothermal conversion efficiencies (PTCEs) up to 90% and a molecule (M2) that is constructed by replacing the amino group of C1TI with an H atom, via excited-state dynamics simulations based on the time-dependent density functional theory (TD-DFT). The simulations reveal fast (<150 fs of average time) nonradiative decays of the lowest excited singlet (S1) state to a conical intersection (CI) with the ground (S0) state in high yields (C1TI: 93.9% and M2: 87.1%). The fast decays, driven by C=N bond rotation to a perpendicular structural configuration, are found to be barrierless. The slight structural difference between C1TI and M2 leads to drastically different S0-S1 energy surfaces, especially M2 features a relatively much lower CI (0.8 eV in energy) and much more decay energy (1.0 eV) to approach the CI. This work provides insights into the de-excitation mechanisms and the performance tuning of C=N enabled photothermal materials.

Adenine ultrafast photorelaxation via electron-driven proton transfer.

Photorelaxation of adenine in water was reported to be ultrafast (within 180 fs) primarily due to radiationless relaxation. However, in the last two decades, several experimental and theoretical investigations on photoexcitation of adenine have revealed diverse types of decay mechanisms. Using time-dependent density functional excited-state nonadiabatic dynamics simulations we show that it is the water to adenine electron-driven proton transfer (EDPT) barrierless reaction responsible for the ultrafast component of the adenine relaxation, which, however, occurred only in the case of the 7H isomer of adenine with five water molecules. This result reveals a known reaction pathway, however not found in previous simulations, with inference for the ultrafast relaxation mechanisms of adenine reported in experiments. The 9H isomer of adenine with six water molecules relaxing in a water cluster followed the previously known structural distortion (C2) decay pathway. The observations of the adenine EDPT reaction with water provide the origin of the experimental ultrafast adenine decay component and present a possible method to tackle future computational challenges in molecular-level biological processes.

Revealing the tunability of electronic structures and optical properties of novel SWCNT derivatives, phenine nanotubes.

Single-walled carbon nanotubes (SWCNTs) have evoked great interest for various luminescent applications, but the large emission heterogeneity resulting from the structural complexity of the samples seriously restricts their further development. Herein we theoretically explore the electronic structures and optical properties of phenine nanotubes (pNTs), which are typical luminescent SWCNT derivatives with determined molecular structures that have been synthesized recently (Z. Sun, K. Ikemoto, T. M. Fukunaga, T. Koretsune, R. Arita, S. Sato and H. Isobe, Science, 2019, 363, 151-155; K. Ikemoto, S. Yang, H. Naito, M. Kotani, S. Sato and H. Isobe, Nat. Commun., 2020, 11, 1807). Interestingly, pNTs are found to feature different semiconducting properties to SWCNTs, as indicated by a spatial separation trend in the HOMO and LUMO resulting from periodic structural vacancies. The HOMO-LUMO and optical gaps of pNTs depend inversely on their lengths and diameters, but diameter variation should be an ineffective method for property tuning due to its negligible influence. By contrast, chemical modifications via N doping or hydrogenation highly affect the HOMO-LUMO gaps and their distributions and greatly broaden the light absorption/emission range, and importantly, low-dose hydrogenation is predicted to be a feasible strategy to enhance luminescence. This work, by studying the fundamental photophysical properties of pNTs and making comparisons to SWCNTs, shows the promise of structural vacancy engineering and surface functionalization in acquiring multifunctional tube-like materials.

Topological-Distortion-Driven Amorphous Spherical Metal-Organic Frameworks for High-Quality Single-Mode Microlasers.

Metal-organic frameworks (MOFs) have recently emerged as appealing platforms to construct microlasers owing to their compelling characters combining the excellent stability of inorganic materials and processable characters of organic materials. However, MOF microstructures developed thus far are generally composed of multiple edge boundaries due to their crystalline nature, which consequently raises significant scattering losses that are detrimental to lasing performance. In this work, we propose a strategy to overcome the above drawback by designing spherically shaped MOFs microcavities. Such spherical MOF microstructures are constructed by amorphizing MOFs with a topological distortion network through introducing flexible building blocks into the growth environment. With an ultra-smooth surface and excellent circular boundaries, the acquired spherical microcavities possess a Q factor as high as ≈104 and can provide sufficient feedback for high-quality single-mode lasing oscillations. We hope that these results will pave an avenue for the construction of new types of flexible MOF-based photonic components.

Laterally Engineering Lanthanide-MOFs Epitaxial Heterostructures for Spatially Resolved Planar 2D Photonic Barcoding.

Metal-organic frameworks (MOFs) heterostructures with domain-controlled emissive colors have shown great potential for achieving high-throughput sensing, anti-counterfeit and information security. Here, a strategy based on steric-hindrance effect is proposed to construct lateral lanthanide-MOFs (Ln-MOFs) epitaxial heterostructures, where the channel-directed guest molecules are introduced to rebalance in-plane and out-of-plane growth rates of the Ln-MOFs microrods and eventually generate lateral MOF epitaxial heterostructures with controllable aspect ratios. A library of lateral Ln-MOFs heterostructures are acquired through a stepwise epitaxial growth procedure, from which rational modulation of each domain with specific lanthanide doping species allows for definition of photonic barcodes in a two-dimensional (2D) domain with remarkably enlarged encoding capacity. The results provide molecular-level insight into the use of modulators in governing crystallite morphology for spatially assembling multifunctional heterostructures.

Hydrogen-Location-Sensitive Modulation of the Redox Reactivity for Oxygen-Deficient TiO2.

Hydrogenated black TiO2 is receiving ever-increasing attention, primarily due to its ability to capture low-energy photons in the solar spectrum and its highly efficient redox reactivity for solar-driven water splitting. However, in-depth physical insight into the redox reactivity is still missing. In this work, we conducted a density functional theory study with Hubbard U correction (DFT+U) based on the model obtained from spectroscopic and aberration-corrected scanning transmission electron microscopy (AC-STEM) characterizations to reveal the synergy among H heteroatoms located at different surface sites where the six-coordinated Ti (Ti6C) atom is converted from an inert trapping site to a site for the interchange of photoexcited electrons. This in-depth understanding may be applicable to the rational design of highly efficient solar-light-harvesting catalysts.

Nonradiative Excited-State Decay via Conical Intersection in Graphene Nanostructures.

Chemical groups are known to tune the luminescent efficiencies of graphene-related nanomaterials, but some species, including the epoxide group (-COC-), are suspected to act as emission-quenching sites. Herein, by performing nonadiabatic excited-state dynamics simulations, we reveal a fast (within 300 fs) nonradiative excited-state decay of a graphene epoxide nanostructure from the lowest excited singlet (S1 ) state to the ground (S0 ) state via a conical intersection (CI), at which the energy difference between the S1 and S0 states is approximately zero. This CI is induced after breaking one C-O bond at the -COC- moiety during excited-state structural relaxation. This study ascertains the role of epoxide groups in inducing the nonradiative recombination of the excited electron-hole, providing important insights into the CI-promoted nonradiative de-excitations and the luminescence tuning of relevant materials. In addition, it shows the feasibility of utilizing nonadiabatic excited-state dynamics simulations to investigate the photophysical processes of the excited states of graphene nanomaterials.

Mechanism of Charge Separation and Frontier Orbital Structure in Graphitic Carbon Nitride and Graphene Quantum Dots.

Graphene quantum dots (GQDs) and carbon nitride quantum dots (CNQDs), the latest addition to the carbon material family, are promising materials for numerous novel applications in optical sensing, photocatalysis, biosensing, and photovoltaics. However, understanding the photocatalytic capability of CNQDs compared to GQDs requires investigations of the charge behavior on the excited state energy surface. In this work, through time-dependent density functional tight binding (TD-DFTB) calculations, we show that CNQDs exhibit superior ground state frontier orbitals (FOs) localization. Strong localization of the FOs and excited state charge separation observed in the first excited state are caused by the relaxation of the structure. Excited energy surface investigations reveal spatial confinement of FOs to the stretched C-N bonds due to excited state structural relaxation. On the other hand, no such localized FOs structure was found for GQDs, presumably caused by its strong π-conjugated configuration not allowing large structural changes upon excitation. The optical absorption and emission of CNQDs is sensitive to size and does not show large variations with the shape of the QD. Our approach provides an explanation for the origin of the enhanced photocatalytic performance of CNQDs over GQDs and their characteristic FOs localization.

Formation Mechanism of Atmospheric Ammonium Bisulfate: Hydrogen-Bond-Promoted Nearly Barrierless Reactions of SO3 with NH3 and H2 O.

Particulate matter (PM) air pollution threatens the health of people and ecosystems worldwide. As the key component of PM, ammonium sulfate plays a critical role in the formation of aerosol particles; thus, there is an urgent need to know the detailed mechanisms for its formation in the atmosphere. Through a quantum chemistry study, we reveal a series of nearly barrierless reactions that may occur in clusters/droplets in the atmosphere leading to the formation of ammonium bisulfate (NH4 HSO4 ), the precursor of ammonium sulfate. In this mechanism, NH4 HSO4 is directly formed through one-step reactions of SO3 with H2 O and NH3 promoted by surrounding molecule(s) that substantially lower the reaction activation barrier to ≈0 kcal mol-1 . The promoters of these reactions are found to be various common atmospheric molecules, such as water, ammonia, and sulfuric acid, which can form relatively strong hydrogen bonds with the reaction center. Our results suggest many more similar pathways that can be facilitated by other ambient molecules. Due to its one-step and barrierless reaction characteristics and the great abundance of potential reactions, this mechanism has great implications on the formation of atmospheric ammonium sulfate as well as on the growth of aerosol particles.

Excited state dynamics study of the self-trapped exciton formation in silicon nanosheets.

The exciton formation dynamics of several model silicon nanosheets (SiNSs) are investigated using a time-dependent density functional tight binding method. The first excited-state (S1) self-trapped exciton formation in the SiNSs is obtained by observing the frontier orbital localization related to the characteristic size of the electronic excitations. The frontier molecular orbitals are highly localized in the S1 state on the stretched Si-Si bond due to the photo-excited structural relaxation, leading to a significant Stokes shift. A time domain study of the photo-excited emission gap correlated with the frontier orbital localization properties for exciton formation. The stretched Si-Si softer bonds provide a favorable site for exciton localization, resulting in exciton trapping. The exciton formation time was found to be around ∼450-850 fs, showing the consistency of the initial exciton formation time with a recent measurement (∼500 to ∼900 fs). This study reveals that Si-Si bond breaking acts as an optical activity center and provides regulation of the self-trapped exciton formation time by the quantum confinement effect in SiNSs; significant to the Si nanomaterial properties.

Transition metal-free one-pot synthesis of fused 1,4-thiazepin-5(4H)-ones and theoretical study of the S-N type smiles rearrangement process.

A series of 1,4-thiazepin-5(4H)-one derivatives were synthesized via a transition metal-free one-pot Smiles rearrangement process at room temperature. Regioselective seven-membered heterocycles were constructed in good to excellent yields. To gain an in-depth understanding of the S-N type Smiles rearrangement mechanism, a theoretical study was also performed by quantum chemistry calculations.

A Reusable Fluorescent Molecular Self-Assembly Cage for Simultaneous Detection and Recycling of Silver(I) Ion.

Although molecular self-assembled porous materials capable of ratiometric fluorescence probing and recycling of metal ions are both economically and environmentally attractive, very few current efforts have been devoted. Herein, we demonstrated a three-dimensional pure organic cage, namely 4-cage, which can serve as a fluorescent probe for simultaneous ratiometric detection and recycling of Ag+ ion. Taking advantage of the promising emission behavior of its rigidified tetraphenylethylene scaffolds and the chelating ability of its dynamically reversible imine moieties, on one hand, upon the addition of Ag+ , 4-cage undergoes coordination to form a stable but poorly soluble fluorescent complex, Ag+ @4-cage, accompanied by a fluorescence color change from bluish-green to yellowish-green. This allows us to differentiate Ag+ from other cations with high selectivity. On the other hand, upon the addition of Cl- anion, Ag+ @4-cage can be effectively converted into free 4-cage due to the competitive coordination of Cl- with Ag+ . Through this process, secondary usage of 4-cage and the recycling of Ag+ ion can be achieved.

Efficient wide-spectrum one-dimensional MWO4 (M = Mn, Co, and Cd) photocatalysts: Synthesis, characterization and density functional theory study.

Broadening the absorption region to near-infrared (NIR) light is critical for the photocatalysis due to the larger proportion and stronger penetration of NIR light in solar energy. In the present paper, one-dimensional (1D) MWO4 (M = Mn, Co, and Cd) materials synthesized by electrospinning technique, were studied by combining the density functional theory (DFT) with experiment results, which possessed the enhanced light absorption capability within the range of 200-2000 nm. It was proved that in the ultraviolet-visible (UV-Vis) region, the absorption bands of CoWO4 and MnWO4 samples were attributed to the metal-to-metal charge transfer mechanism, while the absorption of CdWO4 sample may be referable to the ligand-to-metal charge transfer mechanism. In the near-infrared (NIR) region, the absorption of CoWO4 and MnWO4 primarily originated from the d-d orbital transitions of Mn2+ and Co2+. The photocatalytic experimental results showed that the degradation rates for bisphenol A (BPA) over CoWO4, MnWO4, and CdWO4 photocatalysts under UV-Vis/NIR light irradiation for 140 min/12 h were 78.8 %/75.9 %, 23.8 %/21.3 %, 12.8 %/8.7 %, respectively. This research offers the novel insights into the precise construction of tungstate catalytic systems and contributes to the advancement of UV-Vis-NIR full spectrum photocatalytic technology, and lays a foundation for a cleaner and more environmental-friendly future.

Directional Self-Assembly of Facet-Aligned Organic Hierarchical Super-Heterostructures for Spatially Resolved Photonic Barcodes.

Organic multicolor heterostructures with spatially resolved luminescent colors and identifiable patterns have exhibited considerable potential for achieving micro-/nanoscale photonic barcodes. Nevertheless, such types of barcodes reported thus far are exclusively based on a single heterostructure with limited coding elements. Here, a directional self-assembly strategy is proposed to achieve high-coding-capacity spatially resolved photonic barcodes through rationally constructing organic hierarchical super-heterostructures, where numerous subheterostructure blocks with flat hexagonal facets are precisely oriented with their specific facets via a reconfigurable capillary force. The building blocks were prepared through a one-pot sequential heteroepitaxial growth, which enables the effective modulation of the structural and color characteristics in coding structures. Significantly, a directional facet-to-facet attraction between particles via facet registration leads to the formation of well-defined 1D super-heterostructures, which contain multiple coding elements, thus providing a good platform for constructing the high-coding-capacity photonic barcodes. The results may be useful in fabricating organic hierarchical hybrid super-heterostructures for security labels and optical data recording.

High-Temperature Liquid-Liquid Phase Transition in Glass-Forming Liquid Pd43Ni20Cu27P10.

Liquid-liquid phase transition (LLPT) is a transition from one liquid state to another with the same composition but distinct structural change, which provides an opportunity to explore the relationships between structural transformation and thermodynamic/kinetic anomalies. Herein the abnormal endothermic LLPT in Pd43Ni20Cu27P10 glass-forming liquid was verified and studied by flash differential scanning calorimetry (FDSC) and ab initio molecular dynamics (AIMD) simulations. The results show that the change of the atomic local structure of the atoms around the Cu-P bond leads to the change in the number of specific clusters <0 2 8 0> and <1 2 5 3>, which leads to the change in the liquid structure. Our findings reveal the structural mechanisms that induce unusual heat-trapping phenomena in liquids and advance the understanding of LLPT.

3',6'-Bis(diethyl-amino)-2-[(E)-2-(4-hy-droxy-3-meth-oxy-benzyl-idene-amino)-eth-yl]spiro-[isoindoline-1,9'-xanthen]-3-one ethanol monosolvate.

In the title compound, C(38)H(42)N(4)O(4)·C(2)H(6)O, prepared via a spiro-lactam ring-formation reaction in a rhodamine dye, the xanthene ring system is approximately planar (r.m.s. deviation = 0.0014Å) and subtends dihedral angles of 88.10 (3) and 86.92 (4)° with the spiro-lactam (r.m.s. deviations = 0.0012 Å) and benzene rings, respectively. The crystal structure consists of chains parallel to [-101], formed via O-H⋯O inter-actions.