Spin Orbit Charge Transfer Intersystem Research Articles

Solvent Effects on Spin-Orbit Charge-Transfer Intersystem Crossing in Aryl-Substituted Boron-dipyrromethene Donor-Acceptor Dyads.

In heavy-atom-free organic molecules, the rate of triplet generation through charge recombination, as dictated by the El-Sayed rule, can be enhanced by 101-102 times compared with the rate of spontaneous spin flipping between π-π* orbitals. This mechanism is known as the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). Within the framework of the SOCT-ISC mechanism, facilitating the generation of charge-separated (CS) states and suppressing the spin-allowed direct charge recombination to the ground state are pivotal for maximizing the efficiency of generating localized triplet states. Herein, a series of orthogonal aryl-substituted boron-dipyrromethene dyads were studied by time-resolved spectroscopy to unravel the multichannel competitive relationships in the SOCT-ISC mechanism. The energy level of the electron donor and the stabilization of the solvent effect to the charge-transfer state are reflected in the Gibbs free energy changes of the electron transfer and recombination reactions, leading to significantly different triplet quantum yields. Additionally, solvation-induced electronic coupling changes in excited states lead to the fact that the spin-allowed charge recombination rate cannot be well simply predicted by the Marcus inverted region but has to consider the specific excited-state dynamics in optimizing the proportion of triplet generation channels based on charge recombination.

Constructing Heavy-Atom-Free Photosensitizers for Hypoxic Tumor Phototherapy Based on Donor-Excited Photoinduced Electron-Transfer-Driven Type-I and Type-II Mechanisms.

The spin-orbit charge transfer intersystem crossing (SOCT-ISC) photophysical process has shown great potential for constructing heavy-atom-free photosensitizers (PSs) for photodynamic therapy (PDT) of tumors. However, for almost all such PSs reported to date, the SOCT-ISC is driven by the acceptor-excited photoinduced electron transfer (a-PeT). In this work, for the first time the donor-excited photoinduced electron transfer (d-PeT)-driven SOCT-ISC mechanism is utilized to construct the heavy-atom-free PSs for PDT of tumors by directly installing the electron-deficient N-alkylquinolinium unit (as an electron acceptor) into the meso-position of the near-infrared (NIR) distyryl Bodipy chromophore (as an electron donor). In the less polar environment, the PSs exist as the monomer and promote the production of singlet oxygen (1O2) (Type-II) relying on the d-PeT-driven population of the triplet excited state via SOCT-ISC, whereas in the aqueous environment, they exist as nanoaggregates and induce the generation of superoxides (O2-•) and hydroxyl radicals (HO•) (Type-I) via the d-PeT-driven formation of the delocalized charge-separated state. The PSs could rapidly be internalized into cancer cells and induce the simultaneous production of intracellular 1O2, O2-•, and HO• upon NIR light irradiation, endowing the PSs with superb photocytotoxicity with IC50 values up to submicromolar levels whether under normoxia or under hypoxia. Based on the PSs platform, a tumor-targetable PS is developed, and its abilities in killing cancer cells and in ablating tumors without damage to normal cells/tissues under NIR light irradiation are verified in vitro and in vivo. The study expands the design scope of PSs by introducing the d-PeT conception, thus being highly valuable for achieving novel PSs in the realm of tumor PDT.

Solvent and alkyl substitution effects on charge-transfer mediated triplet state generation in BODIPY dyads: a combined computational and experimental study

Donor–acceptor dyads based on BODIPYs have been recently employed to enhance the formation of triplet excited states with the process of spin–orbit charge transfer intersystem crossing (SOCT-ISC) which does not require introduction of transition metals or other heavy atoms into the molecule. In this work we compare two donor–acceptor dyads based on meso-naphthalenyl BODIPY by combining experimental and computational investigations. The photophysical and electrochemical characterization reveals a significant effect of alkylation of the BODIPY core, disfavoring the SOCT-ISC mechanism for the ethylated BODIPY dyad. This is complemented with a computational investigation carried out to rationalize the influence of ethyl substituents and solvent effects on the electronic structure and efficiency of triplet state population via charge recombination (CR) from the photoinduced electron transfer (PeT) generated charge-transfer (CT) state. Time dependent-density functional theory (TD-DFT) calculations including solvent effects and spin–orbit coupling (SOC) calculations uncover the combined role played by solvent and alkyl substitution on the lateral positions of BODIPY.Graphical abstract

The Rhodamine–Perylene Compact Electron Donor–Acceptor Dyad: Spin-Orbit Charge-Transfer Intersystem Crossing and the Energy Balance of the Triplet Excited States

The Rhodamine–Perylene Compact Electron Donor–Acceptor Dyad: Spin-Orbit Charge-Transfer Intersystem Crossing and the Energy Balance of the Triplet Excited States

Substitution effects on the photoinduced excited state dynamics of perylenemonoimides in solution and thin films.

Perylene monoimide (PMI) derivatives are attracting significant attention due to their strong absorption in the visible range, thermal stability, and synthetic accessibility. These properties make them promising for application in various areas such as optoelectronic devices, photosensitizers, etc. In this work, the photophysical properties and excited state dynamics of four different PMI derivatives (PMIB, BrPMITB, PMITB, and APITB) were studied in solution and thin films utilizing steady-state and time-resolved spectroscopic techniques. Among the four PMI derivatives, APITB is designed as a donor-acceptor dyad, with thianthrene as a donor and PMI as an acceptor. The activation of the triplet state through the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process in THF was observed upon substitution with the thianthrene group at the peri position of the PMI moiety. The SOCT-ISC process facilitates triplet formation in the APITB dyad within 423 ps. Meanwhile, other PMI derivatives showed fluorescence within the femtosecond timescale in THF. The PMI derivatives in thin films displayed different photo physical properties to those in THF. This discrepancy arises due to the effective intermolecular coupling between the PMI derivatives in thin films.

Triphenylphosphonium-functionalized dimeric BODIPY-based nanoparticles for mitochondria-targeting photodynamic therapy.

The dimerization of boron dipyrromethene (BODIPY) moieties is an appealing molecular design approach for developing heavy-atom-free triplet photosensitizers (PSs). However, BODIPY dimer-based PSs generally lack target specificity, which limits their clinical use for photodynamic therapy. This study reports the synthesis of two mitochondria-targeting triphenylphosphonium (TPP)-functionalized meso-β directly linked BODIPY dimers (BTPP and BeTPP). Both BODIPY dimers exhibited solvent-polarity-dependent singlet oxygen (1O2) quantum yields, with maximum values of 0.84 and 0.55 for BTPP and BeTPP, respectively, in tetrahydrofuran. The compact orthogonal geometry of the BODIPY dimers facilitated the generation of triplet excited states via photoinduced charge separation (CS) and subsequent spin-orbit charge-transfer intersystem crossing (SOCT-ISC) processes and their rates were dependent on the energetic configuration between the frontier molecular orbitals of the two BODIPY subunits. The as-synthesized compounds were amphiphilic and hence formed stable nanoparticles (∼36 nm in diameter) in aqueous solutions, with a zeta potential of ∼33 mV beneficial for mitochondrial targeting. In vitro experiments with MCF-7 and HeLa cancer cells indicated the effective localization of BTPP and BeTPP within cancer-cell mitochondria. Under light irradiation, BTPP and BeTPP exhibited robust photo-induced therapeutic effects in both cell lines, with half-maximal inhibitory concentration (IC50) values of ∼30 and ∼55 nM, respectively.

Ambient Phosphor with High Efficiency and Long Lifetime in Poly(Methyl Methacrylate) Through Charge-Transfer-Mediated Triplet Exciton Formation for Photolithography Applications.

Currently, purely organic compounds showing ambient phosphorescence with high efficiency (ΦP ) and ultra-long lifetime (τP ) are quite rare and often need to be achieved in hydrophilic poly(vinyl alcohol)-based hosts. This severely limits their applications. Here, we provide a solution to this issue by constructing an ortho-linked donor-acceptor (D-A) dyad whose D moiety has not only a long-lived T1 state to achieve a long τP , but also a Tn state that is close to the S1 state of the dyad to trigger effective spin-orbit charge transfer intersystem crossing (SOCT-ISC). The rationality of this strategy was validated by a new phosphor OF-BCz that is able to show a τP of 1.92 s and a ΦP of 30 % even in a less rigid matrix of poly(methyl methacrylate) (PMMA). Excitingly, OF-BCz exhibited its potential as both a photocuring initiator and an in situ quality indicator, allowing for the visual detection of defects in photolithographic patterning.

Efficient Spin-Orbit Charge-Transfer Intersystem Crossing and Slow Intramolecular Triplet-Triplet Energy Transfer in Bodipy-Perylenebisimide Compact Dyads and Triads.

Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad were prepared to study the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). For BDP-PBI-3, in which BDP was attached at the imide position of PBI, higher singlet oxygen quantum yield (ΦΔ =85 %) was observed than the bay-substituted derivative BDP-PBI-1 (ΦΔ =30 %). Femtosecond transient absorption spectra indicate slow Förster resonance energy transfer (FRET; 40.4 ps) and charge separation (CS; 1.55 ns) in BDP-PBI-3, while for BDP-PBI-1, CS takes 2.8 ps. For triad BDP-PBI-2, ultrafast FRET (149 fs) and CS (4.7 ps) process were observed, the subsequent charge recombination (CR) takes 5.8 ns and long-lived 3 PBI* (179.8 μs) state is populated. Nanosecond transient absorption spectra of BDP-PBI-3 show that the CR gives upper triplet excited state (3 BDP*) and subsequently, via a slow intramolecular triplet energy transfer (14.5 μs), the 3 PBI* state is finally populated, indicating that upper triplet state is involved in SOCT-ISC. Time-resolved electron paramagnetic resonance spectroscopy revealed that both radical pair ISC (RP ISC) and SOCT-ISC contribute to the ISC. A rare electron spin polarization of (e, e, e, e, e, e) was observed for the triplet state formed via the RP ISC mechanism, due to the S-T+1 /T0 states mixing.

Highly Efficient Photosensitizers with Molecular Vibrational Torsion for Cancer Photodynamic Therapy.

The development of highly effective photosensitizers (PSs) for photodynamic therapy remains a great challenge at present. Most PSs rely on the heavy-atom effect or the spin-orbit charge-transfer intersystem crossing (SOCT-ISC) effect to promote ISC, which brings about additional cytotoxicity, and the latter is susceptible to the interference of solvent environment. Herein, an immanent universal property named photoinduced molecular vibrational torsion (PVT)-enhanced spin-orbit coupling (PVT-SOC) in PSs has been first revealed. PVT is verified to be a widespread intrinsic property of quinoid cyanine (QCy) dyes that occurs on an extremely short time scale (10-10 s) and can be captured by transient spectra. The PVT property can provide reinforced SOC as the occurrence of ISC predicted by the El Sayed rules (1ππ*-3nπ*), which ensures efficient photosensitization ability for QCy dyes. Hence, QTCy7-Ac exhibited the highest singlet oxygen yield (13-fold higher than that of TCy7) and lossless fluorescence quantum yield (ΦF) under near-infrared (NIR) irradiation. The preeminent photochemical properties accompanied by high biosecurity enable it to effectively perform photoablation in solid tumors. The revelation of this property supplies a new route for constructing high-performance PSs for achieving enhanced cancer phototherapy.

Do The Twist: Efficient Heavy-Atom-Free Visible Light Polymerization Facilitated by Spin-Orbit Charge Transfer Inter-system Crossing.

The use of visible light to drive polymerizations with spatiotemporal control offers a mild alternative to contemporary UV-light-based production of soft materials. In this spectral region, photoredox catalysis represents the most efficient polymerization method, yet it relies on the use of heavy-atoms, such as precious metals or toxic halogens. Herein, spin-orbit charge transfer intersystem crossing from boron dipyrromethene (BODIPY) dyads bearing twisted aromatic groups is shown to enable efficient visible light polymerizations in the absence of heavy-atoms. A ≈5-15× increase in polymerization rate and improved photostability was achieved for twisted BODIPYs relative to controls. Furthermore, monomer polarity had a distinct effect on polymerization rate, which was attributed to charge transfer stabilization based on ultrafast transient absorption and phosphorescence spectroscopies. Finally, rapid and high-resolution 3D printing with a green LED was demonstrated using the present photosystem.

BODIPY-Perylene Charge Transfer Compounds; Sensitizers for Triplet-Triplet Annihilation Up-conversion.

BODIPY heterochromophores, asymmetrically substituted with perylene and/or iodine at the 2 and 6 positions were prepared and investigated as sensitizers for triplet-triplet annihilation up conversion (TTA-UC). Single-crystal X-ray crystallographic analyses show that the torsion angle between BODIPY and perylene units lie between 73.54 and 74.51, though they are not orthogonal. Both compounds show intense, charge transfer absorption and emission profiles, confirmed by resonance Raman spectroscopy and consistent with DFT calculations. The emission quantum yield was solvent dependent but the emission profile remained characteristic of CT transition across all solvents explored. Both BODIPY derivatives were found to be effective sensitizers of TTA-UC with perylene annihilator in dioxane and DMSO. Intense anti-Stokes emission was observed, and visible by eye from these solvents. Conversely, no TTA-UC was observed from the other solvents explored, including from non-polar solvents such as toluene and hexane that yielded brightest fluorescence from the BODIPY derivatives. In dioxane, the power density plots obtained were strongly consistent with TTA-UC and the power density threshold, the Ith value (the photon flux at which 50 % of ΦTTAUC is achieved), for B2PI was observed to be 2.5x lower than of B2P under optimal conditions, an effect ascribed to the combined influence of spin-orbit charge transfer intersystem crossing (SOCT-ISC) and heavy metal on the triplet state formation for B2PI.

Spin–orbit charge transfer intersystem crossing and thermal activation delayed fluorescence (TADF) studies of compact orthogonal anthraquinone phenothiazine derivatives

Thermally activated delayed fluorescence (TADF) in compact electron donor–acceptor dyads has attracted great attention due to their potential application in organic light-emitting diodes.

Spin-orbit charge-transfer intersystem crossing in heavy-atom-free orthogonal covalent boron-dipyrromethene heterodimers.

Boron-dipyrromethene (BODIPY) derivatives are prospective organic-based triplet photosensitizers. Since the triplet generation yield of the parent BODIPY is low, heavy atoms are widely used to improve the triplet yield. However, the dimerization of BODIPYs can also significantly improve their ability to produce triplets. Through a comparative study of the triplet formation dynamics of two heavy-atom-free orthogonal covalent BODIPY heterodimers that differ in their dihedral angles, we have demonstrated that the mechanism of spin-orbit charge-transfer intersystem crossing (SOCT-ISC) promotes the triplet generation of BODIPY heterodimers in solution. Different from the general understanding of SOCT-ISC, the heterodimer with a smaller dihedral angle and low structural rigidity showed better triplet generation due to (a) the stronger inter-chromophoric interaction in the heterodimer, which promoted the formation of a solvent-stabilized charge-transfer (CT) state, (b) the more favorable energy level alignment with sizeable spin-orbit coupling strength, and (c) the balance between the stabilized singlet CT state and limited direct charge recombination to the ground state in a weakly polar solvent. The complete spectral characterization of the triplet formation dynamics clarified the SOCT-ISC mechanism and important factors affecting the triplet generation in BODIPY heterodimers.

A type I and II compatible vinyl-pyridine modified BODIPY dimer photosensitizer for photodynamic therapy in A-549 cells.

In this paper, the vinyl-pyridine group was used to modify the BODIPY dimer photosensitizer (T-BDP2) to obtain a VP-BDP2 photosensitizer. Compared with the T-BDP2 photosensitizer, the VP-BDP2 photosensitizer could work under pure water conditions, the singlet oxygen yield was increased from 9.38% to 22.2%, the charge transfer rate was increased from about 30 ps to about 10 ps, and the red emission was enhanced in fluorescence imaging. In addition, the VP-BDP2 photosensitizer could also generate the superoxide radical (O2˙-) under pure water conditions. The ROS generation mechanism of the VP-BDP2 photosensitizer was considered to be the spin-orbit charge-transfer intersystem crossing (SOCT-ISC) mechanism, which was verified by fs-transient absorption spectra and theoretical calculation. In the photodynamic therapy of A-549 cells, the VP-BDP2 photosensitizers could generate singlet oxygen and superoxide radicals (O2˙-) under biological conditions, and showed high phototoxicity with the IC50 value at 12.1 μM under light at 525 nm. Additionally, the multiple dipolar configuration meant that the VP-BDP2 photosensitizer could be used in two-photon fluorescence zebrafish imaging under 800 nm excitation, which sets the stage for future two-photon photodynamic therapy.

Mechanism of Ultrafast Triplet Exciton Formation in Single Cocrystals of π-Stacked Electron Donors and Acceptors.

Ultrafast triplet formation in donor-acceptor (D-A) systems typically occurs by spin-orbit charge-transfer intersystem crossing (SOCT-ISC), which requires a significant orbital angular momentum change and is thus usually observed when the adjacent π systems of D and A are orthogonal; however, the results presented here show that subnanosecond triplet formation occurs in a series of D-A cocrystals that form one-dimensional cofacial π stacks. Using ultrafast transient absorption microscopy, photoexcitation of D-A single cocrystals, where D is coronene (Cor) or pyrene (Pyr) and A is N,N-bis(3'-pentyl)-perylene-3,4:9,10-bis(dicarboximide) (C5PDI) or naphthalene-1,4:5,8-tetracarboxydianhydride (NDA), results in formation of the charge transfer (CT) excitons Cor•+-C5PDI•-, Pyr•+-C5PDI•-, Cor•+-NDA•-, and Pyr•+-NDA•- in <300 fs, while triplet exciton formation occurs in τ = 125, 106, 484, and 958 ps, respectively. TDDFT calculations show that the SOCT-ISC rates correlate with charge delocalization in the CT exciton state. In addition, time-resolved EPR spectroscopy shows that Cor•+-C5PDI•- and Pyr•+-C5PDI•- recombine to form localized 3*C5PDI excitons with zero-field splittings of |D| = 1170 and 1250 MHz, respectively. In contrast, Cor•+-NDA•- and Pyr•+-NDA•- give triplet excitons in which |D| is only 1240 and 690 MHz, respectively, compared to that of NDA (2091 MHz), which is the lowest energy localized triplet exciton, indicating that the Cor-NDA and Pyr-NDA triplet excitons have significant CT character. These results show that charge delocalization in CT excitons impacts both ultrafast triplet formation as well as the CT character of the resultant triplet states.

An Approach to Developing Cyanines with Upconverted Photosensitive Efficiency Enhancement for Highly Efficient NIR Tumor Phototheranostics.

Upconverted reactive oxygen species (ROS) photosensitization with one-photon excitation mode is a promising tactic to elongate the excitation wavelengths of photosensitive dyes to near-infrared (NIR) light region without the requirement of coherent high-intensity light sources. However, the photosensitization efficiencies are still finite by the unilateral improvement of excited-state intersystem crossing (ISC) via heavy-atom-effect, since the upconverted efficiency also plays a decisive role in upconverted photosensitization. Herein, a NIR light initiated one-photon upconversion heavy-atom-free small molecule system is reported. The meso-rotatable anthracene in pentamethine cyanine (Cy5) is demonstrated to enrich the populations in high vibrational-rotational energy levels and subsequently improve the hot-band absorption (HBA) efficiency. Moreover, the spin-orbit charge transfer intersystem crossing (SOCT-ISC) caused by electron donated anthracene can further amplify the triplet yield. Benefiting from the above two aspects, the 1 O2 generation significantly increases with over 2-fold improved performance compared with heavy-atom-modified method under upconverted light excitation, which obtains efficient in vivo phototheranostic results and provides new opportunities for other applications such as photocatalysis and fine chemical synthesis.

Naphthalimide-Carbazole Compact Electron Donor-Acceptor Dyads: Effect of Molecular Geometry and Electron-Donating Capacity on the Spin-Orbit Charge Transfer Intersystem Crossing.

We prepared a series of naphthalimide (NI)-carbazole (Cz) compact electron donor-acceptor dyads showing different substitution positions, C-N/C-C linkers, and conformation restriction magnitudes to study the spin-orbit charge transfer intersystem crossing (SOCT-ISC). The varied conformation restrictions lead to different dihedral angles between the donor and acceptor (37°-81°) and electronic coupling magnitude (matrix elements V: 1290-3070 cm-1). Based on the comparison between the dyads containing C-N and C-C linkers, we found that a large dihedral angle between the donor and acceptor is favorable to efficient SOCT-ISC. For one dyad, the singlet oxygen quantum yield (ΦΔ) is up to 84.4% (in dichloromethane), which is much higher than that of the previously reported NI-phenothiazine (PTZ) analogue dyad (ΦΔ = 16.0% in n-hexane). The intrinsic triplet state lifetime (τT) is 270 μs, longer than that accessed by the heavy atom effect (75.2 μs). As compared with the NI-PTZ analogue dyad, the Cz unit in the current dyads is a weaker electron donor than PTZ. Thus, a higher CT state energy in NI-Cz dyads was observed, which makes the SOCT-ISC efficient in solvents with a wide range of polarities. Meanwhile, the localized triplet state (3LE) becomes the lowest-lying state in the NI-Cz dyads, which is different from the triplet charge transfer (3CT) state observed in the analogue NI-PTZ dyad. Moreover, the large energy gap between the CT and 3LE states inhibits the reverse ISC; as a result, no thermally activated delayed fluorescence was observed for the current NI-Cz dyads.

Heavy Atom-Free, Mitochondria-Targeted, and Activatable Photosensitizers for Photodynamic Therapy with Real-Time In-Situ Therapeutic Monitoring.

Based on spin-orbit charge transfer intersystem crossing mechanism, two heavy-atom-free photosensitizers (PSs) BDP1/BDP2 with absorption maxima at 506 nm/660 nm were constructed for photodynamic therapy (PDT). The long triplet state lifetimes and large singlet oxygen quantum yields, coupled with the mitochondria-targeted feature, made them highly phototoxic toward cancer cells. Moreover, the PDT-promoted cell apoptosis could be monitored by an obvious fluorescence off-on response of the two PSs due to the concomitant activation of extensive mitophagy, thus facilitating timely therapeutic feedback to avoid under- or over-treatment. Importantly, such design allows the activatable PSs Glu-BDP1/Glu-BDP2 to be fabricated by attaching γ-glutamyl, a substrate of γ-glutamyltranspeptidase, to the alkoxyaniline unit of BDP1/BDP2, and their ability in either selectively killing cancer cells over normal cells or in ablating implanted tumour without damage to healthy tissue was demonstrated.

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene-Dimethylaniline.

The conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin–orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin–orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin–orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

Efficient symmetry breaking spin–orbit charge transfer-induced intersystem crossing in compact orthogonal perylene-phenothiazine or -phenoxazine triads and observation of the delayed fluorescence

For the first time, efficient spin–orbit charge transfer intersystem crossing (ΦΔ = 70%) is attained via the symmetry-breaking charge transfer approach in newly designed perylene orthogonal triads.