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Visible-to-near-infrared light-harvesting A-π-D-π-A porphyrins, ZnP-CPDT and ZnP-BT are proved to be highly efficient in photocatalytic hydrogen evolution (PHE) with the highest PHE rate (ηH2) of 1.80 mmol g−1 h−1 for ZnP-CPDT.

Intramolecular charge and energy transfer processes initiated by light absorption can change the photosensitization properties of molecular conjugates. Transient optical and electron paramagnetic resonance (TREPR) spectroscopies are well suited for the study of these processes. In the TREPR spectra of the triplet state of an iodinated BODIPY dimer, we have observed the effect of the averaging of the zero-field (ZFS) parameter

A twisted π-conjugated framework does not necessarily promote efficacious ISC, energy matching of S1/Tn excited states offers a more promising route to triplet enhancement.

We prepared a rhodamine-TEMPO chromophore-radical dyad (RB-TEMPO) to study the radical enhanced intersystem crossing (REISC). The visible light-harvesting chromophore rhodamine is connected with the TEMPO (a nitroxide radical) via a C–N bond. The UV-vis absorption spectrum indicates negligible electron interaction between the two units at the ground state. Interestingly, the fluorescence of the rhodamine moiety is strongly quenched in RB-TEMPO, and the fluorescence lifetime of the rhodamine moiety is shortened to 0.29 ns, from the lifetime of 3.17 ns. We attribute this quenching effect to the intramolecular electron spin–spin interaction between the nitroxide radical and the photoexcited rhodamine chromophore. Nanosecond transient absorption spectra confirm the REISC in RB-TEMPO, indicated by the detection of the rhodamine chromophore triplet excited state; the lifetime was determined as 128 ns, which is shorter than the native rhodamine triplet state lifetime (0.58 μs). The zero-field splitting (ZFS) parameters of the triplet state of the chromophore were determined with the pulsed laser excited time-resolved electron paramagnetic resonance (TREPR) spectra. RB-TEMPO was used as a photoinitiator for the photopolymerization of pentaerythritol triacrylate (PETA). These studies are useful for the design of heavy atom-free triplet photosensitizers, the study of the ISC, and the electron spin dynamics of the radical-chromophore systems upon photoexcitation.

Naphthalimide (NI) homo- and hetero-dimers adopting orthogonal geometry were prepared to study photo-induced symmetry-breaking charge transfer (SBCT) and charge recombination (CR)-induced intersystem crossing (ISC). The two moieties in the dimer are connected either at the 3-C or 4-C position of the NI unit. The photophysical properties of the dimers were studied with steady-state and transient absorption spectroscopic methods. Significant CT only occurs for the hetero-dimer, in which one NI unit has a 4-amino substituent and the other NI unit is without it. The CR-induced ISC is most efficient for this dimer (singlet oxygen quantum yield ?= 50.3%). For the homo-dimer, in which both NI units did not present amino substitution, SBCT was not observed. Based on the electrochemical studies, we propose that the absence of SBCT for the homo-dimer is attributed to its high oxidation potential and low reduction potential. Femtosecond transient absorption (fs TA) spectra show that there is no charge separation (CS) for the homo-dimer. Nanosecond transient absorption spectroscopy indicate the formation of a triplet state with electron delocalization for the homo dimer, with a lifetime of 72.0 ?s, while for the hetero dimer a triplet state with an intrinsic lifetime of 206.4 ?s is observed. CS (11.6 ps) and slow CR-induced ISC (>1.5 ns) were observed for the hetero-dimer. Time-resolved electron paramagnetic resonance spectra give the zero-field splitting parameters (|D| = 1894 MHz and |E| = 111 MHz) and electron spin polarization patterns (e, e, e, a, a, a) for the triplet state of the hetero-dimer, inferring that the triplet state of the hetero-dimer is confined on the amino-substituted NI moiety.

A series of naphthalimide (NI)-phenothiazine (PTZ) electron donor-acceptor dyads were prepared to study the thermally activated delayed fluorescence (TADF) property of the dyads, from a point of view of detection of the various transient species. The photophysical properties of the dyads were tuned by changing the electron donating and the electron withdrawal capability of the PTZ and NI moieties, respectively, by oxidation of the PTZ unit, or by using different arylamines to attach with the NI unit. This tuning effect was manifested in the UV-vis absorption and fluorescence emission spectra, e.g., the change of the charge transfer absorption bands. TADF was observed for the dyads containing native PTZ unit, and the prompt and delayed fluorescence lifetimes changed when different arylamine was used. In polar solvent, no TADF was observed. For the dyads with the PTZ unit oxidized, no TADF was observed as while. Femtosecond transient absorption spectra show that the charge separation takes ca. 0.6 ps, and admixture of locally excited (3LE) state and charge separated (1CS/3CS) states formed (in n-hexane). The subsequent charge recombination from the 1CS state takes ca. 7.92 ns. Upon oxidation of the PTZ unit, the beginning of charge separation is at 178 fs, and formation of 3LE state takes 4.53 ns. Nanosecond transient absorption (ns-TA) spectra show that both 3CS and 3LE states were observed for the dyads showing TADF, whereas only 3LE or 3CS state was observed for the systems lacking of TADF. This is a rare but unambiguous experimental evidence that the spin-vibronic coupling of 3CS/ 3LE states is crucial for TADF. Without the mediating effect of the 3LE state, no TADF is resulted, even the long-lived 3CS state is populated (lifetime τCS ≈ 140 ns). This experimental result confirms the 3CS → 1CS reverse intersystem crossing (rISC) is slow, without coupling with an approximate 3LE state. These studies are useful for in-depth understanding of the photophysical mechanisms of the TADF emitters, as well as for molecular structure design of new electron donor-acceptor TADF emitters.

A long-lived triplet charge separated state (

A facile scenario is proposed to design DBA-type molecules with E(T2) > E(S1) ≥ 2E(T1), promising to realize 200% exciton utilization through a three-step mechanism for organic electroluminescence.

A new Ir-complex conjugated porphyrin exhibits AIE property for the Ir-complex unit, inhibition of ACQ of the porphyrin unit and efficient energy transfer from the Ir-complex to the porphyrin, therefore, enhanced photocatalytic H2 evolution.

The photophysical insights of thermally activated delayed fluorescence emitters for OLEDs obtained by time-resolved EPR spectroscopy were summarized.

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.

Naphthalimide (NI) conjugated Pt(ii)-porphyrins show high performances in cocatalyst-free photocatalytic hydrogen evolution (PHE) because of their long-lived excited states and strong light-harvesting capability.

Intersystem crossing was observed for diaminoanthraquinone via transient absorption spectroscopy and the compounds were used as novel initiators for photopolymerization.

With phenoxazine (PXZ) as the electron donor and perylene-3,4-dicarboximide (PMI) as the electron acceptor, we prepared a compact, orthogonal electron donor-acceptor dyad (PMI-PXZ) to study the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC). A weak charge transfer (CT) absorption band, due to S0 → 1CT transition, was observed (e = 2840 M-1 cm-1 at 554 nm, FWHM: 2850 cm-1), which is different from that of the previously reported analogue dyad with phenothiazine as the electron donor (PMI-PTZ), for which no CT absorption band was observed. A long-lived triplet state was observed (lifetime τT = 182 μs) with nanosecond transient absorption spectroscopy, and the singlet oxygen quantum yield (ΦΔ = 76%) is higher than that of the previously reported analogue dyad PMI-PTZ (ΦΔ = 57%). Ultrafast charge separation (ca. 0.14 ps) and slow charge recombination (1.4 ns) were observed with femtosecond transient absorption spectroscopy. With time-resolved electron paramagnetic resonance spectroscopy (TREPR), we confirmed the SOCT-ISC mechanism, and the electron spin polarization phase pattern of the triplet-state TREPR spectrum is (e, e, a, e, a, a), which is dramatically different from that of PMI-PTZ (a, e, a, e, a, e), indicating that the triplet-state TREPR spectrum of a specific chromophore in the electron donor-acceptor dyads is not only dependent on the geometry of the dyads but also dependent on the structure of the electron donor (or acceptor). Even one-atom variation in the donor structure may cause significant influence on the electron spin selectivity of the ISC of the electron donor-acceptor dyads.

Weakening the triplet-triplet annihilation (TTA) self-quenching effect induced by sensitizers remains a tremendous challenge due to the very few investigations carried out on them. Herein, benzo-21-crown-7 (B21C7)-functionalized 2,6-diiodo-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (DIBDP) was synthesized to investigate the influences of huge bulks and electron-rich cavities of B21C7 moieties on the fluorescence emission and triplet-state lifetimes of DIBDP moieties. Density functional theory (DFT)/time-dependent DFT (TDDFT) computable results preliminarily predicted that B21C7 moieties had influences on the fluorescence emissions of DIBDP moieties but not on their localization of triplet states of B21C7-functionalized DIBDP (B21C7-DIBDP). The UV-vis absorption spectra, fluorescence emission spectra, and cyclic voltammograms verified that there was an electron-transfer process from the B21C7 moiety to the DIBDP moiety in B21C7-DIBDP. However, the calculated results of ΔGCS and ECS values and nanosecond time-resolved transient absorption spectra demonstrated that the electron-transfer process from the B21C7 moiety to the DIBDP moiety in B21C7-DIBDP had direct influences on the fluorescence emission of DIBDP moieties but not on the triplet states of DIBDP moieties. The experimental values of triplet-state lifetimes of B21C7-DIBDP were obviously longer than those of DIBDP at a high concentration (1.0 × 10-5 M); however, the fitted values of intrinsic triplet-state lifetimes of B21C7-DIBDP were slightly greater than those of DIBDP in the same solvent. These results demonstrated that the steric hindrance of B21C7 moieties could weaken the TTA self-quenching effect of DIBDP moieties at a high concentration and the a-PET effect induced a proportion of the produced singlet states of DIBDP moieties and could not emit fluorescence in the form of radiation transition but they could be transformed into triplet states through intersystem crossing (ISC) processes due to the iodine atoms in the DIBDP moiety. The stronger a-PET effects in polar solvents induced smaller fluorescence quantum yields so that more singlet states of DIBDP moieties were transformed into triplet states to weaken the TTA self-quenching effects.

The photophysical processes involved in the electron donor-acceptor thermally activated delayed fluorescence (TADF) of emitters are complicated and controversial. The recent consensus is that at least three states are involved, i.e. the singlet charge transfer state (1CT), the triplet localized excited state (3LE) and the triplet CT state (3CT). It is clear the very often used steady state and time-resolved luminescence spectroscopic methods are unable to present direct evidence for the dark states, i.e. the 3LE and 3CT states, as well as the interconversion of these states. Concerning this aspect, the femtosecond-nanosecond transient absorption spectroscopic methods are in particular interests. Both the emissive state and the dark state can be detected in these spectra, and interconversion of the states involved in TADF process can be also revealed. This review article focuses on the recent development of using the transient absorption spectra to study the photophysics of the TADF emitters.

A series of 2-phenylquinoxaline ligands have been synthesised that introduce either CF3 or OCF3 electron-withdrawing groups at different positions of the phenyl ring. These ligands were investigated as cyclometalating reagents for platinum(II) to give neutral complexes of the form [Pt(C^N)(acac)] (in which C^N=cyclometalating ligand; acac=acetyl acetonate). X-ray crystallographic studies on three examples showed that the complexes adopt an approximate square planar geometry. All examples revealed strong Pt−Pt linear contacts of 3.2041(6), 3.2199(3) and 3.2586(2) Å. The highly coloured complexes display efficient visible absorption at 400–500 nm (ϵ ≈5000 M−1 cm−1) and orange red photoluminescent characteristics (λem=603–620 nm; Φem ≤37 %), which were subtly tuned by the ligand. Triplet emitting character was confirmed by microsecond luminescence lifetimes and the photogeneration of singlet oxygen with quantum efficiencies up to 57 %. Each complex was investigated as a photosensitiser for triplet–triplet annihilation energy upconversion using 9,10-diphenylanthracene as the annihilator species: a range of good upconversion efficiencies (ΦUC 5.9–14.1 %) were observed and shown to be strongly influenced by the ligand structure in each case.

Understanding the impact of the excited state wavefunction confinement is crucial for the engineering of the photophysical properties and applications of organic chromophores. In the present contribution, the localization of the triplet state wavefunctions of some symmetric ethyne/butadiyne bridged BODIPY dimers and asymmetric BODIPY derivatives presenting extended π-conjugation frameworks is studied with time-resolved electron paramagnetic resonance spectroscopy and time-dependent density functional theory computations. Based on the Zero Field Splitting D parameters, we conclude that the triplet state wavefunctions are highly localized on one BODIPY unit in the symmetric dimers, which is consistent with the ab initio modelling that finds delocalized triplet state destabilized by 12-14 kcal mol

Three anthracene (An)-naphthalenediimide (NDI) compact electron donor-acceptor dyads were prepared. Femtosecond transient absorption (fs-TA) spectra show fast charge separation (ca. 0.9-1.7 ps) and relatively slow charge recombination (ca. 8-565 ps) upon photoexcitation; moreover, the

Photocatalysis is a facile strategy for complex chemical transformations. Heterogeneous photocatalysis, especially in the flow system, has attracted much attention as it avoids the separation of catalysts. Herein, a kind of a Bodipy-containing porous microcapsule heterogeneous photocatalyst was rationally constructed with modulation on a multiscale. The diiodo-Bodipy with methacrylate (MA-2IBDP) was synthesized as a polymerizable photosensitizer. After immobilization in a polymer matrix, the intersystem crossing rate constant of MA-2IBDP increased to 2.7 × 1010 s-1 and its triplet excited-state lifetime prolonged to ∼1 ms. Porous structures in microcapsules were created to facilitate mass transfer. A flat plate flow reactor was constructed to fix the catalytic microcapsules and improve light utilization. With the combination of all the above benefits, the reaction rate constant (0.896 s-1) is 10 times faster than that of MA-2IBDP in a homogeneous system for juglone synthesis. The continuous production can last for 30 h without yield decrease. The photocatalyst can also be used in aza-Henry reaction, Alder-Ene reaction, and oxidation of thiols to disulfides with conversion rates above 95%. This study provides a means for the construction of heterogeneous catalysts and the flow reaction system.