Intersystem Crossing and Electron Spin Selectivity in Anthracene-Naphthalimide Compact Electron Donor-Acceptor Dyads Showing Different Geometry and Electronic Coupling Magnitudes.

Anthracene-naphthalimide (An-NI) compact electron donor-acceptor dyads were prepared, in which the orientation and distance between the two subunits were varied by direct connection or with intervening phenyl linker. Efficient intersystem crossing (ISC) and long triplet state lifetime (ΦΔ =92 %, τT =438 µs) were observed for the directly connected dyads showing a perpendicular geometry (81°). This efficient spin-orbit charge transfer ISC (SOCT-ISC) takes 376 fs, inhibits the direct charge recombination (CR) to ground state (1 CT→S0 , takes 3.04 ns). Interestingly, efficient SOCT-ISC for dyads with intervening phenyl linker (ΦΔ =40 % in DCM) was also observed, although the electron donor and acceptor adopt almost coplanar geometry (dihedral angle: 15°). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy shows that the electron spin polarization of the triplet state, i. e. the electron spin selectivity of ISC, is highly dependent on the dihedral angle and the linker. For the dyads showing weaker coupling between the donor and acceptors, the charge separation and the intramolecular triplet energy transfer are inhibited at 80 K (frozen solution), because both the 3 An and 3 NI states were observed and the ESP are same as compared to the native anthracene and naphthalimide, which unravel their origin. The dyads were used as triplet photosensitizers for triplet-triplet annihilation upconversion (TTA UC). High UC quantum yield (ΦUC =12.9 %) as well as a large anti-Stokes shift (0.72 eV) was attained by excitation into the CT absorption band.

Efficient Intersystem Crossing in the Tröger's Base Derived From 4-Amino-1,8-naphthalimide and Application as a Potent Photodynamic Therapy Reagent.

Intersystem crossing (ISC) was observed for naphthalimide (NI)-derived Tröger's base, and the ISC was confirmed to occur by a spin-orbital charge-transfer (SOCT) mechanism. Conventional electron donor/acceptor dyads showing SOCT-ISC have semirigid linkers. In contrast, the linker between the two chromophores in Tröger's base is rigid and torsion is completely inhibited, which is beneficial for efficient SOCT-ISC. Femtosecond transient absorption (TA) spectra demonstrated charge-separation and charge-recombination-induced ISC processes. Nanosecond TA spectroscopy confirmed the ISC, and the triplet state is long-lived (46 µs, room temperature). The ISC quantum yield is dependent on solvent polarity (8-41 %). The triplet state was studied by pulsed-laser-excited time-resolved EPR spectroscopy, and both the NI-localized triplet state and triplet charge-transfer state were observed, which is in good agreement with the spin-density analysis. The Tröger's base was confirmed to be a potent photodynamic therapy reagent with HeLa cells (EC50 =5.0 nm).

Anthryl-Appended Platinum(II) Schiff Base Complexes: Exceptionally Small Stokes Shift, Triplet Excited States Equilibrium, and Application in Triplet-Triplet-Annihilation Upconversion.

Two anthryl platinum(II) N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-benzenediamine Schiff base complexes were synthesized, with the anthryl attached via its 9 position (Pt-9An) or 2 position (Pt-2An) to the platinum (Pt) Schiff base backbone. The complexes show unusually small Stokes shifts (0.23 eV), representing a very small energy loss for the photoexcitation/intersystem crossing process, which is beneficial for applications as triplet photosensitizers. Phosphorescence of the Pt(II) coordination framework (ΦP = 11.0%) is quenched in the anthryl-containing complexes (ΦP = 4.0%) and shows a biexponential decay (τP = 3.4 µs/87% and 18.2 µs/13%) compared to the single-exponential decay of the native Pt(II) Schiff base complex (τP = 3.7 µs). Femtosecond/nanosecond transient absorption spectroscopy suggests an equilibrium between triplet anthracene (3An) and triplet metal-to-ligand charge-transfer (3MLCT) states, with the dark 3An state slightly lower in energy (1.96 eV for Pt-9An and 1.90 eV for Pt-2An) than the emissive 3MLCT state (1.97 eV for Pt-9An and 1.91 eV for Pt-2An). Intramolecular triplet-triplet energy transfer (TTET) and reverse TTET take 4.8 ps/444 ps for Pt-9An and 55 ps/1.7 ns for Pt-2An, respectively. The triplet-state equilibrium extends the triplet-state lifetime of the complexes to 103 µs (Pt-2An) or 163 µs (Pt-9An), in comparison to the native Pt(II) complex, which shows a lifetime of 4.0 µs. The complexes were used for triplet-triplet-annihilation upconversion with perylene as the triplet acceptor. The upconversion quantum yield is up to 15%, and a large anti-Stokes shift (0.75 eV) is achieved by excitation into the singlet metal-to-ligand charge-transfer absorption band (589 nm) of the complexes (anti-Stokes shift is 0.92 eV with 9,10-diphenylanthracene as the acceptor).

Anthracene-Naphthalenediimide Compact Electron Donor/Acceptor Dyads: Electronic Coupling, Electron Transfer, and Intersystem Crossing.

We attached different electron donors of phenyl, anthryl, and alkylamino moieties, to electron acceptor naphthalenediimide (NDI) to construct compact electron donor/acceptor dyads. The purpose is to study the effect of electron coupling (the magnitude is the matrix element, VDA) on the photophysical properties of UV-vis absorption, fluorescence emission, especially spin-orbit charge transfer intersystem crossing. We found that the magnitude of VDA depends on the electron donating strength of the aryl moieties ( VDA = 0.22-0.55 eV), as well as the molecular conformation, based on steady state and time-resolved transient absorption spectroscopies. We also found that electron coupling does not show the add-up (or synergetic) effect. Solvent polarity-dependent intersystem crossing (ISC) was observed for the dyad/triads and singlet oxygen quantum yield decreases in polar solvents. Femtosecond transient absorption results indicate that the charge separation (CS) for 9-An-NDI-NH occurs on time scale of 0.83 ps (in toluene) or 0.71 ps (in acetonitrile). The charge recombination (CR) process (50 ps in toluene) produces triplet state with ΦISC = 19%. The triplet state lifetime is up to 22 µs. This result indicates that orthogonal geometry for a compact electron donor/acceptor does not lead to efficient ISC via CR. Other factors such as the energy gap between the CS state and triplet state also determine the ISC efficiency.

Ligand-Tuneable, Red-Emitting Iridium(III) Complexes for Efficient Triplet-Triplet Annihilation Upconversion Performance.

A series of substituted 2-phenylquinoxaline ligands have been explored to finely tune the visible emission properties of a corresponding set of cationic, cyclometallated iridium(III) complexes. The electronic and redox properties of the complexes were investigated through experimental (including time-resolved luminescence and transient absorption spectroscopy) and theoretical methods. The complexes display absorption and phosphorescent emissions in the visible region that are attributed to metal to ligand charge-transfer transitions. The different substitution patterns of the ligands induce variations in these parameters. Time-dependent DFT studies support these assignments and show that there is likely to be a strong spin-forbidden contribution to the visible absorption bands at λ=500-600 nm. Calculations also reliably predict the magnitude and trends in triplet emitting wavelengths for the series of complexes. The complexes were assessed as potential sensitisers in triplet-triplet annihilation upconversion experiments by using 9,10-diphenylanthracene as the acceptor; the methylated variants performed especially well with impressive upconversion quantum yields of up to 39.3 %.

Recent progress in heavy atom-free organic compounds showing unexpected intersystem crossing (ISC) ability.

In this review, recent progress in heavy atom-free triplet photosensitizers was summarized. The general approaches include attaining S1/Tn states sharing similar energy levels or proper molecular geometry to satisfy the angular momentum reservation in intersystem crossing (ISC). ISC via the higher singlet excited state (Sn, n > 1) → Tm (m > 1), which is a rarely reported phenomenon, was also discussed. The ISC of some Bodipy dimers was proposed to be via the 'doubly excited state', but recent studies show that the ISC mechanism of these Bodipy dimers is charge separation/recombination. These new findings in the study of triplet photosensitizers are useful for photovoltaics, photodynamic therapy and photocatalysis, as well as in fundamental photochemistry studies.

Microscopic Three-Dimensional Measurement Based on Telecentric Stereo and Speckle Projection Methods.

Three-dimensional (3D) measurement of microstructures has become increasingly important, and many microscopic measurement methods have been developed. For the dimension in several millimeters together with the accuracy at sub-pixel or sub-micron level, there is almost no effective measurement method now. Here we present a method combining the microscopic stereo measurement with the digital speckle projection. A microscopy experimental setup mainly composed of two telecentric cameras and an industrial projection module is established and a telecentric binocular stereo reconstruction procedure is carried out. The measurement accuracy has firstly been verified by performing 3D measurements of grid arrays at different locations and cylinder arrays with different height differences. Then two Mitutoyo step masters have been used for further verification. The experimental results show that the proposed method can obtain 3D information of the microstructure with a sub-pixel and even sub-micron measuring accuracy in millimeter scale.

Triplet Excited State of BODIPY Accessed by Charge Recombination and Its Application in Triplet-Triplet Annihilation Upconversion.

The triplet excited state properties of two BODIPY phenothiazine dyads (BDP-1 and BDP-2) with different lengths of linker and orientations of the components were studied. The triplet state formation of BODIPY chromophore was achieved via photoinduced electron transfer (PET) and charge recombination (CR). BDP-1 has a longer linker between the phenothiazine and the BODIPY chromophore than BDP-2. Moreover, the two chromophores in BDP-2 assume a more orthogonal geometry both at the ground and in the first excited state (87°) than that of BDP-1 (34-40°). The fluorescence of the BODIPY moiety was significantly quenched in the dyads. The charge separation (CS) and CR dynamics of the dyads were studied with femtosecond transient absorption spectroscopy (kCS = 2.2 × 1011 s-1 and 2 × 1012 s-1 for BDP-1 and BDP-2, respectively; kCR = 4.5 × 1010 and 1.5 × 1011 s-1 for BDP-1 and BDP-2, respectively; in acetonitrile). Formation of the triplet excited state of the BODIPY moiety was observed for both dyads upon photoexcitation, and the triplet state quantum yield depends on both the linker length and the orientation of the chromophores. Triplet state quantum yields are 13.4 and 97.5% and lifetimes are 13 and 116 µs for BDP-1 and BDP-2, respectively. The spin-orbit charge transfer (SO-CT) mechanism is proposed to be responsible for the efficient triplet state formation. The dyads were used for triplet-triplet annihilation (TTA) upconversion, showing an upconversion quantum yield up to 3.2%.

Using Wavelet Packet Transform for Surface Roughness Evaluation and Texture Extraction.

Surface characterization plays a significant role in evaluating surface functional performance. In this paper, we introduce wavelet packet transform for surface roughness characterization and surface texture extraction. Surface topography is acquired by a confocal laser scanning microscope. Smooth border padding and de-noise process are implemented to generate a roughness surface precisely. By analyzing the high frequency components of a simulated profile, surface textures are separated by using wavelet packet transform, and the reconstructed roughness and waviness coincide well with the original ones. Wavelet packet transform is then used as a smooth filter for texture extraction. A roughness specimen and three real engineering surfaces are also analyzed in detail. Profile and areal roughness parameters are calculated to quantify the characterization results and compared with those measured by a profile meter. Most obtained roughness parameters agree well with the measurement results, and the largest deviation occurs in the skewness. The relations between the roughness parameters and noise are analyzed by simulation for explaining the relatively large deviations. The extracted textures reflect the surface structure and indicate the manufacturing conditions well, which is helpful for further feature recognition and matching. By using wavelet packet transform, engineering surfaces are comprehensively characterized including evaluating surface roughness and extracting surface texture.

Sparse Reconstruction for Micro Defect Detection in Acoustic Micro Imaging.

Acoustic micro imaging has been proven to be sufficiently sensitive for micro defect detection. In this study, we propose a sparse reconstruction method for acoustic micro imaging. A finite element model with a micro defect is developed to emulate the physical scanning. Then we obtain the point spread function, a blur kernel for sparse reconstruction. We reconstruct deblurred images from the oversampled C-scan images based on l1-norm regularization, which can enhance the signal-to-noise ratio and improve the accuracy of micro defect detection. The method is further verified by experimental data. The results demonstrate that the sparse reconstruction is effective for micro defect detection in acoustic micro imaging.

Recent advances in the development of DprE1 inhibitors using AI/CADD approaches.

Tuberculosis (TB) is a global lethal disease caused by Mycobacterium tuberculosis (Mtb). The flavoenzyme decaprenylphosphoryl-ß-d-ribose 2'-oxidase (DprE1) plays a crucial part in the biosynthesis of lipoarabinomannan and arabinogalactan for the cell wall of Mtb and represents a promising target for anti-TB drug development. Therefore, there is an urgent need to discover DprE1 inhibitors with novel scaffolds, improved bioactivity and high drug-likeness. Recent studies have shown that artificial intelligence/computer-aided drug design (AI/CADD) techniques are powerful tools in the discovery of novel DprE1 inhibitors. This review provides an overview of the discovery of DprE1 inhibitors and their underlying mechanism of action and highlights recent advances in the discovery and optimization of DprE1 inhibitors using AI/CADD approaches.

Efficient Photooxidation of Sulfides with Amidated Alloxazines as Heavy-atom-free Photosensitizers.

Photooxidation utilizing visible light, especially with naturally abundant O2 as the oxygen source, has been well-accepted as a sustainable and efficient procedure in organic synthesis. To ensure the intersystem crossing and triplet quantum yield for efficient photosensitization, we prepared amidated alloxazines (AAs) and investigated their photophysical properties and performance as heavy-atom-free triplet photosensitizers and compared with those of flavin (FL) and riboflavin tetraacetate (RFTA). Because of the difference in the framework structure of AAs and FL and the introduction of carbonyl moiety, the absorption of FL at ∼450 nm is blue-shifted to ∼380 nm and weakened (ε = 8.7 × 103 for FL to ∼6.8 × 103 M-1 cm-1), but the absorption at ∼340 nm is red-shifted to ∼350 nm and enhanced by ∼50% (from ε = 6.4 × 103 for FL to ∼9.9 × 103 M-1 cm-1) in AAs. The intersystem crossing rates from the S1 to T1 are also enhanced in these AAs derivatives, while the fluorescence quantum yield decreases from ∼30 to ∼7% for FL and AAs, respectively, making the triplet excited state lifetime and the singlet oxygen quantum yield of AAs at least comparable to those of FL and RFTA. We examined the performance of these heave-atom-free chromophores in the photooxidation of sulfides to afford sulfoxides. In accordance with the prolonged triplet excited state lifetime and enhanced triplet quantum yield, 2-5-fold performance enhancements were observed for AAs in the photooxidation of sulfides with respect to FL. We proposed that the key reactive oxygen species of AA-sensitized photooxidation are singlet oxygen and superoxide radical anion based on mechanistic investigations. The research highlights the superior performance of AAs in photocatalysis and would be helpful to rationalize the design of efficient heavy-atom-free organic photocatalysts.

Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet-triplet annihilation upconversion.

Efficient triplet photosensitizers are important for fundamental photochemical studies and applications such as triplet-triplet annihilation upconversion (TTA UC), photoredox catalytic organic reactions and photovoltaics. We now report a series of phosphorus corrole compounds as efficient visible light-harvesting metal-free triplet photosensitizers. While the heavy-atom-free phosphorus corroles show absorption in the visible spectral region (centered at 573 nm) and have a decent triplet state quantum yield (Φ Δ = 49%), iodo-substitution on the corrole core induces red-shifted absorption (589 nm) and improves intersystem crossing significantly (Φ Δ = 67%). Nanosecond transient absorption spectra confirm triplet state formation upon photoexcitation (τ T = 312 µs) and the iodinated derivatives also display near IR phosphorescence in fluid solution at room temperature (λ em = 796 nm, τ p = 412 µs). Both singlet oxygen (1O2) and superoxide radical anions (O2 -˙) may be produced with the phosphorus corroles, which are competent photocatalysts for the oxidative coupling of benzylamine (the Aza Henry reaction). Very efficient TTA UC was observed with the phosphorus corroles as triplet photosensitizers and perylene as the triplet acceptor, with upconversion quantum yields of up to Φ UC = 38.9% (a factor of 2 was used in the equation) and a very large anti-Stokes effect of 0.5 eV.

Bodipy Derivatives as Triplet Photosensitizers and the Related Intersystem Crossing Mechanisms.

Recently varieties of Bodipy derivatives showing intersystem crossing (ISC) have been reported as triplet photosensitizers, and the application of these compounds in photocatalysis, photodynamic therapy (PDT), and photon upconversion are promising. In this review we summarized the recent development in the area of Bodipy-derived triplet photosensitizers and discussed the molecular structural factors that enhance the ISC ability. The compounds are introduced based on their ISC mechanisms, which include the heavy atom effect, exciton coupling, charge recombination (CR)-induced ISC, using a spin converter and radical enhanced ISC. Some transition metal complexes containing Bodipy chromophores are also discussed. The applications of these new triplet photosensitizers in photodynamic therapy, photocatalysis, and photon upconversion are briefly commented on. We believe the study of new triplet photosensitizers and the application of these novel materials in the abovementioned areas will be blooming.

Hetero-bichromophore Dyad as a Highly Efficient Triplet Acceptor for Polarity Tuned Triplet-Triplet Annihilation Upconversion.

Triplet-triplet annihilation upconversion (TTA UC) was intensively investigated for developing efficient photosensitizers and emitters. But an emission wavelength tunable TTA UC system with only one emitter was rarely reported. A novel hetero-bichromophore dyad, HB-An, showing solvatochromic emission and high fluorescence quantum yields in weakly polar solvents (such as n-hexane, dichloromethane (DCM), and so on) was used as triplet energy acceptor/emitter for polarity tuned TTA UC. A high TTA UC quantum yield up to 25% was achieved and the UC emission wavelengths can be fine-tuned from cyan to yellow by changing the media polarity. This information will be useful for constructing efficient emitting-light-tunable TTA UC system.