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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.

In order to investigate the joint influence of the conformation flexibility and the matching of the energies of the charge-transfer (CT) and the localized triplet excited (3LE) states on the thermally activated delayed fluorescence (TADF) in electron donor–acceptor molecules, a series of compact electron donor–acceptor dyads and a triad were prepared, with naphthalimide (NI) as electron acceptor and phenothiazine (PTZ) as electron donor. The NI and PTZ moieties are either directly connected at the 3-position of NI and the N-position of the PTZ moiety via a C–N single bond, or they are linked through a phenyl group. The tuning of the energy order of the CT and LE states is achieved by oxidation of the PTZ unit into the corresponding sulfoxide, whereas conformation restriction is imposed by introducing ortho-methyl substituents on the phenyl linker, so that the coupling magnitude between the CT and the 3LE states can be controlled. The singlet oxygen quantum yield (ΦΔ) of NI-PTZ is moderate in n-hexane (HEX, ΦΔ = 19%). TADF was observed for the dyads, the biexponential luminescence lifetime are 16.0 ns (99.9%)/14.4 μs (0.1%) for the dyad and 7.2 ns (99.6%)/2.0 μs (0.4%) for the triad. Triplet state was observed in the nanosecond transient absorption spectra with lifetimes in the 4–48 μs range. Computational investigations show that the orthogonal electron donor–acceptor molecular structure is beneficial for TADF. These calculations indicate small energetic difference between the 3LE and 3CT states, which are helpful for interpreting the ns-TA spectra and the origins of TADF in NI-PTZ, which is ultimately due to the small energetic difference between the 3LE and 3CT states. Conversely, NI-PTZ-O, which has a higher CT state and bears a much more stabilized 3LE state, does not show TADF.

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.

In order to study the effect of mutual orientation of the chromophores in compact electron donor-acceptor dyads on the spin-orbit charge transfer intersystem crossing (SOCT-ISC), we prepared naphthalimide (NI)-pyrene (Py) compact electron donor-acceptor dyads, in which pyrene acts as an electron donor and NI is an electron acceptor. The connection of the two units is at the 4-C and 3-C positions of the NI unit and the 1-position of the pyrene moiety for dyads NI-Py-1 and NI-Py-2, respectively. A charge transfer absorption band was observed for both dyads in the UV-vis absorption spectra. Upon nanosecond pulsed laser excitation, long-lived triplet states (lifetime is 220 μs) were observed and the triplet state was confined to the pyrene moiety. The ISC efficiency is moderate to high in nonpolar to polar solvents (singlet oxygen quantum yield: ΦΔ = 14-52%). Ultrafast charge separation (ca. 0.81 ps) and charge recombination-induced ISC (∼3.0 ns) were observed by femtosecond transient absorption spectroscopy. Time-resolved electron paramagnetic resonance spectroscopy confirms the SOCT-ISC mechanism; interestingly, the observed electron spin polarization pattern of the triplet state is chromophore orientation-dependent; and the population rates of the triplet sublevels of NI-Py-1 (Px:Py:Pz = 0.2:0.8:0) are drastically different from those of NI-Py-2 (Px:Py:Pz = 0:0:1).

Three Ni-Al2O3 catalysts were prepared, in planetary ball-milling machine, by the mechanochemical method with Al(NO3)3·9H2O as the aluminum precursor, (NH4)2CO3 as the precipitant, and Ni(NO3)2·6H2O, NiCl2·6H2O, and Ni(CH3COO)2·4H2O as nickel precursors (the corresponding catalysts were labeled as Ni-NO, Ni-Cl, and Ni-Ac). The prepared catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR), and N2 adsorption–desorption technologies, and CO methanation performance evaluation was carried out for the catalysts. Results showed that the catalyst with Ni(NO3)2·6H2O as the precursor presented good Ni dispersibility and a small Ni grain size of 6.80 nm. CO conversion, CH4 selectivity, and yield of the catalyst were as high as 78.8, 87.9, and 69.8%, respectively. Carbon deposition analysis from temperature-programmed hydrogenation (TPH) characterization showed that the H2 consumption peak area of the three samples followed the order: Ni-NO (2886.66 au) < Ni-Cl (4389.97 au) < Ni-Ac (5721.65 au), indicating that the Ni-NO catalyst showed higher resistance to carbon deposition, which might be due to its small Ni grain size.

The photophysical properties, especially the intersystem crossing (ISC) of two heavy-atom-free BODIPY derivatives with twisted π-conjugated frameworks (benzo[b]-fused BODIPY, BDP-B; and [a]phenanthrene-fused BODIPY, BDP-P), are studied with steady-state and time-resolved optical and electron paramagnetic resonance (TREPR) spectroscopic methods as well as with ADC(2) theoretical investigations. Interestingly, BDP-B has a planar π-conjugation framework, but it displays weaker UV-vis absorption (ε = 3.8 × 104 M-1 cm-1 at 569 nm) and fluorescence (ΦF < 0.1%), a short-lived singlet-excited state (fluorescence lifetime, τF = 0.2 ns), and a long-lived triplet state (τT = 132.3 μs). In comparison, the more twisted BDP-P shows stronger UV-vis absorption (ε = 9.8 × 104 M-1 cm-1 at 640 nm) and fluorescence (ΦF = 70%), longer singlet-excited-state lifetime (τF = 6.4 ns), and shorter triplet-state lifetime (τT = 18.9 μs). In contrast to helicenes (ΦT = ca. 90%), the ISC of BDP-P and BDP-B is nonefficient (ΦT < 23%). The electron spin selectivity of the ISC of the derivatives is different, manifested by the phase pattern of the TREPR spectra as AAEAEE and EEEAAA for BDP-B and BDP-P, respectively. The spatially confined T1 state wave function of the twisted molecule keeps the T1 state energy high (1.44-1.61 eV). A dark S1 state was identified for BDP-B. This work demonstrated that the twisted π-conjugated framework does not necessarily induce efficient ISC and we found a dark singlet state for BODIPY, which is rare. ispartof: JOURNAL OF PHYSICAL CHEMISTRY B vol:125 issue:23 pages:6280-6295 ispartof: location:United States status: published

Spiro compact rhodamine-naphthalenediimide electron donor–acceptor dyads show a long-lived charge separated state (lifetime: 0.72 μs) based on the electron spin control effect were reported.

The efficient and selective photocatalytic conversion of chemicals with visible light and naturally abundant resources has long been desired, but this requires finely designed sensitizers that are capable of converting light into chemical energy for the required energy/electron transfer, bond formation and scission

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

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.

A simple heteroleptic iridium(III) photosensitizer, Ir-1, containing two ligands 5-(trifluoromethyl)-2-phenylpyridine (ĈN–CF3) and bipyridine (NN) has for the first time been studied for cocatalys...

The electronic structure and photophysical properties of a series of N-methyl and N-acetyl substituted alloxazines (AZs) were investigated with extensive density functional theory (DFT) and time-dependent density functional theory (TD–DFT) based calculations. We showed that non-radiative decays from the lowest singlet and triplet excited states of these AZs are dominant over their radiative counterparts. The fast non-radiative decays of the excited AZs can be attributed to the energy consumption (Ereorg) through structural reorganization facilitated by the intrinsic normal modes of the alloxazine framework, as well as their coupling with those of the functional groups. Substitution with functional groups may lead to further perturbation of the electronic structure of the AZ chromophore, which may enhance intersystem crossing with the ππ* states of the AZs. Due to the different bonding of N1 and N3 within the alloxazine framework, substitution may result in AZs with different photophysical properties. Specifically, functionalization at N1 may help in maintaining or even reducing Ereorg and would promote the absorption and radiative decay from the excited AZs. However, the strong coupling of the vibrational modes of acetyl at N3 with the intrinsic normal modes of the alloxazine framework would contribute significantly to Ereorg, and benefit the non-radiative decay of the excited AZs. We expect that the findings would pave the way for rational design of novel AZs with extraordinary photophysical properties.

Two novel Ru(II) photosensitisers sporting ethynyl-Nile Red chromophores are shown to absorb strongly in the visible region, and to have two distinct but weakly emissive states (1ILCT* and 3MLCT*). In addition a long-lived, lower energy ‘dark’ (non-emissive) triplet excited state is identified (3ILCT*) and successfully exploited for singlet oxygen generation.

We prepared an orthogonal electron donor/acceptor dyad (NI–Py) with perylene (Py) as electron donor and 4-aminonaphthalimide (NI) as an electron acceptor. The molecule adopts orthogonal geometry due to the steric hindrance exerted by the 4-amino substituents on the NI moiety. The photophysical properties of dyad were studied by steady-state UV–Vis absorption and fluorescence spectroscopies, femtosecond/nanosecond transient absorption spectroscopies and DFT computations. Ground state interaction between the NI and Py units is negligible; however, charge separation occurs upon photoexcitation, indicated by the quenching of the fluorescence of the dyad in polar solvents, i.e. fluorescence quantum yield (ΦF) is 61.9% in toluene and ΦF = 0.2% in methanol. Spin–orbit-coupled charge transfer-induced intersystem crossing (SOCT-ISC) was confirmed by femtosecond transient absorption spectroscopy (charge separation takes 1.7 ps and charge recombination takes 6.9 ns, in CH2Cl2). Nanosecond transient absorption spectra indicated the formation of perylene-localized triplet state, and the triplet state lifetime (175 μs) is much longer than that accessed with the heavy atom effect (3-bromoperylene; 16 μs). The singlet oxygen quantum (ΦΔ) yield of the dyad is 2.2% in hexane and 9.5% in dichloromethane. The low SOCT-ISC efficiency as compared to the previously reported analogue (ΦΔ = 80%) is attributed to the mismatch of the 1CT/Tn state energies, and/or the orientation of the NI and Py units, i.e. orthogonal geometry is not sufficient for achieving efficient SOCT-ISC in compact electron donor/acceptor dyads.