Acridinedione-phthalimide conjugates: Intramolecular electron transfer and singlet oxygen generation studies for optical and photodynamic therapy applications.

We reported herein the synthesis, characterization of hybrid conjugates composed of phthalimide (Phth) and acridine-1,8-diones (Acr) for optical and medical applications. For the synthetic procedure, a three-step synthetic strategy has been utilized. The optical properties of the examined 1,8-acridinedione-phthalimide connected molecules (AcrPhth 1-5) have been examined utilizing various spectroscopic techniques, e.g., steady-state absorption and fluorescence, and time-correlated single photon counting. The steady-state absorption studies showed that AcrPhth 1-5 absorbs the light in the UV and visible region. The fluorescence studies of AcrPhth 1-5 exhibited significant fluorescence quenching compared to the acridinedione control compounds (Acr 1-5) suggesting the occurrence of electron-transfer reactions from the electron donating acridinedione moiety (Acr) to the electron accepting phthalimide moiety (Phth). The rate and efficiency of the electron-transfer reactions were determined from the fluorescence lifetime measurements indicating the fast electron-transfer processes of the covalently connected AcrPhth 1-5 conjugates. Computational studies supported the intramolecular electron-transfer reaction of AcrPhth conjugates using ab initio B3LYP/6-311G methods. In the optimized structures, the HOMO was found to be entirely located on the Acr entity, while the LUMO was found to be entirely on the Phth entity. Further, the synthesized compounds were tested as photosensitizers for generating the singlet oxygen species, which is a key factor in the photodynamic therapy (PDT) applications. The nanosecond laser flash measurements enable us to detect the triplet-excited states of examined Acr and AcrPhth conjugates, determining the triplet quantum yields, and direct detecting the singlet oxygen in an accurate way. From this observation, the singlet quantum yields were found to be in the range of 0.12-0.27 (for Acr 1-5) and 0.07-0.19 (for AcrPhth 1-5 conjugates). The molecular docking studies revealed that compound AcrPhth 2 exhibited high binding affinity with for key genes (p53, TOP2B, p38, and EGFR) suggesting its potential as a targeted anticancer therapy.

Optical Properties of Cationic Perylenediimide Nanowires in Aqueous Medium: Experimental and Computational Studies.

Cationic perylenediimide derivative, namely N,N'-di(2-(trimethylammoniumiodide)ethylene) perylenediimide (TAIPDI), has been synthesized and characterized in an aqueous medium by using dynamic light scattering (DLS), X-ray diffraction (XRD), fourier-transform infrared (FTIR), scanning electron microscope (SEM), and high-resolution transmission electron microscopy (HRTEM) techniques. The optical absorption and fluorescence spectra of TAIPDI revealed the formation of aggregated TAIPDI nanowires in water, but not in organic solvents. In order to control the aggregation behavior, the optical properties of TAIPDI have been examined in different aqueous media, namely cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS). Furthermore, the utilization of the examined TAIPDI for constructing supramolecular donor-acceptor dyad has been achieved by combining the electron accepting TAIPDI with the electron donating 4,4'-bis (2-sulfostyryl)-biphenyl disodium salt (BSSBP). The formed supramolecular dyad TAIPDI-BSSBP through the ionic and electrostatic π-π interactions have been well examined by various spectroscopic techniques, e.g., steady-state absorption and fluorescence, cyclic voltammetry, and time-correlated single-photon counting (TCSPC), and first principle computational chemistry methods. Experimental results suggested the occurring of intra-supramolecular electron transfer from BSSBP to TAIPDI with rate constant and efficiency of 4.76 × 109 s-1 and 0.95, respectively. The ease of construction, absorption in the UV-Visible region, and fast electron transfer process render the supramolecular TAIPDI-BSSBP complex as a donor-acceptor material for optoelectronic devices.

Use of Singlet Oxygen in the Generation of a Mononuclear Nonheme Iron(IV)-Oxo Complex.

Nonheme iron(III)-superoxo intermediates are generated in the activation of dioxygen (O2) by nonheme iron(II) complexes and then converted to iron(IV)-oxo species by reacting with hydrogen donor substrates with relatively weak C-H bonds. If singlet oxygen (1O2) with ca. 1 eV higher energy than the ground state triplet oxygen (3O2) is employed, iron(IV)-oxo complexes can be synthesized using hydrogen donor substrates with much stronger C-H bonds. However, 1O2 has never been used in generating iron(IV)-oxo complexes. Herein, we report that a nonheme iron(IV)-oxo species, [FeIV(O)(TMC)]2+ (TMC = tetramethylcyclam), is generated using 1O2, which is produced with boron subphthalocyanine chloride (SubPc) as a photosensitizer, and hydrogen donor substrates with relatively strong C-H bonds, such as toluene (BDE = 89.5 kcal mol-1), via electron transfer from [FeII(TMC)]2+ to 1O2, which is energetically more favorable by 0.98 eV, as compared with electron transfer from [FeII(TMC)]2+ to 3O2. Electron transfer from [FeII(TMC)]2+ to 1O2 produces an iron(III)-superoxo complex, [FeIII(O2)(TMC)]2+, followed by abstracting a hydrogen atom from toluene by [FeIII(O2)(TMC)]2+ to form an iron(III)-hydroperoxo complex, [FeIII(OOH)(TMC)]2+, that is further converted to the [FeIV(O)(TMC)]2+ species. Thus, the present study reports the first example of generating a mononuclear nonheme iron(IV)-oxo complex with the use of singlet oxygen, instead of triplet oxygen, and a hydrogen atom donor with relatively strong C-H bonds. Detailed mechanistic aspects, such as the detection of 1O2 emission, the quenching by [FeII(TMC)]2+, and the quantum yields, have also been discussed to provide valuable mechanistic insights into understanding nonheme iron-oxo chemistry.

Redox-Active Azulene-based 2D Conjugated Covalent Organic Framework for Organic Memristors.

As a conjugated and unsymmetric building block composed of an electron-poor seven-membered sp2 carbon ring and an electron-rich five-membered carbon ring, azulene and its derivatives have been recognized as one of the most promising building blocks for novel electronic devices due to its intrinsic redox activity. By using 1,3,5-tris(4-aminophenyl)-benzene and azulene-1,3-dicarbaldehyde as the starting materials, an azulene(Azu)-based 2D conjugated covalent organic framework, COF-Azu, is prepared through liquid-liquid interface polymerization strategy for the first time. The as-fabricated Al/COF-Azu/indium tin oxide (ITO) memristor shows typical non-volatile resistive switching performance due to the electric filed induced intramolecular charge transfer effect. Associated with the unique memristive performance, a simple convolutional neural network is built for image recognition. After 8 epochs of training, image recognition accuracy of 80 % for a neutral network trained on a larger data set is achieved.

BSA Interaction, Molecular Docking, and Antibacterial Activity of Zinc(II) Complexes Containing the Sterically Demanding Biomimetic N3S2 Ligand: The Effect of Structure Flexibility.

Two zinc(II) complexes, DBZ and DBZH4, that have (ZnN3S2) cores and differ in the bridging mode of the ligating backbone, effectively bind to BSA. The binding affinity varies as DBZ > DBZH4 and depends on the ligand structure. At low concentrations, both complexes exhibit dynamic quenching, whereas at higher concentrations they exhibit mixed (static and dynamic) quenching. The energy transfer mechanism from the BSA singlet excited state to DBZ and DBZH4, is highly likely according to steady-state fluorescence and time-correlated singlet photon counting. Molecular docking was used to support the mode of interaction of the complexes with BSA and showed that DBZ had more energy for binding. Furthermore, antibacterial testing revealed that both complexes were active but to a lesser extent than chloramphenicol. In comparison to DBZH4, DBZ has higher antibacterial activity, which is consistent with the binding constants, molecular docking, and particle size of adducts. These findings may have an impact on biomedicine.

Self-assembly of porphyrin on graphene oxide in aqueous medium: fabrication, characterization, and photocatalytic studies.

We herein report the supramolecular self-assembly of a water soluble porphyrin, namely, 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin-tetra(p-toluenesulfonate) (TMPyP), on the surface of graphene oxide (GO). The fabricated GO nanosheet and GO@TMPyP hybrid material composite have been characterized by using various spectroscopic and analytical techniques, e.g., scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared (FT-IR) spectroscopy. The steady state absorption measurements of the GO@TMPyP self-assembly showed a significant red shift (∼20 nm) compared to those of the control TMPyP in water. The steady state fluorescence measurements showed a significant fluorescence quenching of the singlet excited state of TMPyP in the presence of GO. These findings suggest the electron transfer reaction from TMPyP to GO. The time resolved fluorescence measurements showed a considerable decrease in the lifetime of the singlet state of TMPyP in the presence of GO, from which the rate and efficiency of the electron transfers from TMPyP to GO were determined to be 1.93 × 109 s-1 and 91%, respectively. The transient absorption measurements showed a considerable quenching of the triplet excited state of TMPyP in the self-assembly. All these findings confirm the occurrence of efficient electronic interactions between TMPyP and GO in both the ground and excited states. In addition, the fabricated GO@TMPyP showed high photocatalytic activity for the degradation of methylene blue (MB) and methyl orange (MO) mixed dye pollutants in water under visible light irradiation.

Long-Lived Photoexcited State of a Mn(IV)-Oxo Complex Binding Scandium Ions That is Capable of Hydroxylating Benzene.

Photoexcitation of a MnIV-oxo complex binding scandium ions ([(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2) in a solvent mixture of trifluoroethanol and acetonitrile (v/v = 1:1) resulted in formation of the long-lived photoexcited state, which can hydroxylate benzene to phenol. The photohydroxylation of benzene by [(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2 was made possible by electron transfer from benzene to the long-lived 2 E excited state of [(Bn-TPEN)MnIV(O)]2+-(Sc(OTf)3)2 to produce a benzene radical cation, which reacted with water as revealed by laser-induced transient absorption measurements.

Assemblies of Boron Dipyrromethene/Porphyrin, Phthalocyanine, and C60 Moieties as Artificial Models of Photosynthesis: Synthesis, Supramolecular Interactions, and Photophysical Studies.

A series of light-harvesting conjugates based on a zinc(II) phthalocyanine core with either two or four boron dipyrromethene (BODIPY) or porphyrin units have been synthesized and characterized. The conjugation of BODIPY/porphyrin units can extend the absorptions of the phthalocyanine core to cover most of the visible region. Upon addition of an imidazole-substituted C60 (C60 Im), it can axially bind to the zinc(II) center of the phthalocyanine core through metal-ligand interactions. The resulting complexes form photosynthetic antenna-reaction center mimics in which the BODIPY/porphyrin units serve as the antennas to capture the light and transfer the energy to the phthalocyanine core by efficient excitation energy transfer. The excited phthalocyanine is then quenched by the axially bound C60 Im moiety by electron transfer, which has been supported by computational studies. The photoinduced processes of the assemblies have been studied in detail by various steady-state and time-resolved spectroscopic methods. By femtosecond transient absorption spectroscopic studies, the lifetimes of the charge-separated state of the bis(BODIPY) and bis(porphyrin) systems have been determined to be 3.2 and 4.0 ns, respectively.

Intramolecular electron transfer of light harvesting perylene-pyrene supramolecular conjugate.

Electronic interactions between the cationic N,N'-bis(2(trimethylammonium iodide) ethylene)perylene-3,4,9,10-tetracarboxyldiimide (TAIPDI) with two electron donors, namely, pyrene (Py) and 1-pyrenesulfonic acid sodium salt (PySA), have been investigated. The spectroscopic studies showed the formation of the supramolecular conjugate between TAIPDI and PySA via ionic interaction, but not with Py. Density functional theory (DFT) combined with a natural energy decomposition analysis (NEDA) technique showed an S-like structure of the supramolecular conjugate TAIPDI-PySA via an ionic interaction. The formation constant of the TAIPDI-PySA supramolecular conjugate was determined to be 3.0 × 104 M-1, suggesting a fairly stable complex formation. The excited state events were monitored by both steady state and time-resolved emission techniques. Upon excitation, the quenching pathways via the singlet-excited states of TAIPDI and PySA involved the intramolecular electron transfer from the electron donating PySA to the electron accepting TAIPDI with a rate constant of 1.10 × 1011 s-1 and a quantum yield of 0.99. The thermodynamic parameters of the supramolecular TAIPDI-PySA conjugate have been determined using the stopped-flow technique.

A light harvesting perylene derivative - zinc phthalocyanine complex in water: spectroscopic and thermodynamic studies.

A perylene derivative, namely N,N'-bis(2(trimethylammonium iodide)ethylene)perylene-3,4,9,10-tetracarboxyldiimide (TAIPDI) forms nanoscale columnar stacks in water that have been characterized by using optical absorption and emission measurements, dynamic light scattering (DLS), and transmission electron microscopy (TEM). This behaviour was compared with that of unstacked TAIPDI in methanol. Assembly formation between the one-dimensional TAIPDI stacks and zinc phthalocyanine tetrasulphonic groups (ZnPcS4) via strong π-π and ionic interactions has been described in an aqueous medium. The formation constant of the supramolecular dyad has been determined as 2.94 × 104 M-1 from both the absorption and fluorescence measurements. Upon addition of ZnPcS4, the fluorescence quenching of the singlet-excited state of TAIPDI was observed because of the electron transfer process from ZnPcS4 to TAIPDI via the singlet-excited states of ZnPcS4 and TAIPDI entities. The electrochemical studies supported the electron transfer pathways via the singlet states of ZnPcS4 and TAIPDI. The thermodynamic parameters of the supramolecular complex have been determined from stopped-flow measurements. The interaction between ZnPcS4 and TAIPDI occurs in two steps, where the rate constant of the second step with TAIPDI (207 ± 8 M-1 s-1) is much slower than the first one (3515 ± 101 M-1 s-1). Activation parameters for the complex formation (ΔH# = 76 ± 11 kJ mol-1 and ΔS# = 83 ± 37 J K-1 mol-1, and ΔH# = 221 ± 15 kJ mol-1 and ΔS# = 540 ± 50 J K-1 mol-1) were determined from variable temperature studies for the first and second steps, respectively. The significantly positive ΔS# values found for both steps of the interaction reactions are consistent with a dissociative mechanism.

A subphthalocyanine-pyrene dyad: electron transfer and singlet oxygen generation.

A light harvesting subphthalocyanine-pyrene dyad has been synthesized and characterized by linking pyrene (Py) with subphthalocyanine (SubPc) at its axial position with the B-O bond through the para position of the benzene group. Upon photoexcitation at the pyrene unit of the dyad, an efficient electron transfer from the singlet-excited state of Py to SubPc was observed. The electron transfer features were also observed by exciting the SubPc entity, but with slower rates (∼108 s-1). From the electrochemical measurements, the negative driving forces for charge separation via both the singlet states of Py and SubPc in the polar solvents indicate that the electron transfer is thermodynamically feasible. Interestingly, the examined compounds showed relatively high efficiency for producing the singlet oxygen (ΦΔ = ∼0.70). The collected data suggested the usefulness of the examined subphthalocyanine-pyrene dyad as a model of light harvesting system, as well as a sensitizer for photodynamic therapy.

Light-Harvesting Phthalocyanine-Diketopyrrolopyrrole Derivatives: Synthesis, Spectroscopic, Electrochemical, and Photochemical Studies.

A new family of light-harvesting zinc phthalocyanine (ZnPc)-diketopyrrolopyrrole (DPP) hybrids have been synthesized and characterized. The absorption spectral measurements showed that the major absorptions of DPP (450-600 nm) are complementary to those of zinc phthalocyanine (300-400 and 600-700 nm). Therefore, the designed hybrids absorb over a broad range in the visible region. The geometric and electronic structures of the dyads were probed by initio B3LYP/6-311G methods. The majority of the HOMOs were found to be located on the ZnPc, while the majority of the LUMOs were on the DPP units. The DPP units serve as the antenna, which upon excitation undergo efficient singlet-singlet energy transfer to the attached ZnPc units. The formed singlet ZnPc, in turn, donates its electron to the electron-deficient DPP forming the low-lying radical ion pairs ZnPc.+ -DPP.- (energy=1.44-1.56 eV as calculated from the electrochemical measurements). The excited-state events were confirmed by using a transient absorption technique in the picosecond-microsecond time range, as well as a time-resolved emission technique. The rates of energy transfer from the singlet DPP to ZnPc were found to be extremely fast >1010  s-1 , while the rates of electron transfer from the singlet excited state of ZnPc to DPP were found to be 3.7-6.6×109  s-1 .

Light harvesting a gold porphyrin-zinc phthalocyanine supramolecular donor-acceptor dyad.

We reported herein the spectroscopic, electrochemical and laser photolysis studies for the newly constructed light harvesting supramolecular dyad composed of gold porphyrin (AuPpy), as an electron acceptor, and zinc phthalocyanine (ZnPc), as an electron donor, to mimic the reaction centre in the photosynthetic system. For this, gold porphyrin has been functionalized by pyridine units, which axially coordinated with zinc phthalocyanine to form the stable supramolecular AuPpy:ZnPc with a rate of 2.94 × 104 M-1. Steady-state fluorescence measurements showed significant quenching of the singlet excited ZnPc emission with addition of AuPpy, suggesting an electron transfer from the singlet excited ZnPc to AuPpy. The electron transfer character was confirmed by recoding the characteristic absorption band of the zinc phthalocyanine radical cation in the NIR region by a femtosecond laser photolysis technique. The findings that the AuPpy:ZnPc supramolecular dyad exhibits relatively long-lived radical-ion pairs and absorbs light in a wide range of the solar spectrum suggest that it would be useful as a photosynthetic reaction centre.

Photosynthetic antenna-reaction center mimicry by using boron dipyrromethene sensitizers.

Various molecular and supramolecular systems have been synthesized and characterized recently to mimic the functions of photosynthesis, in which solar energy conversion is achieved. Artificial photosynthesis consists of light-harvesting and charge-separation processes together with catalytic units of water oxidation and reduction. Among the organic molecules, derivatives of BF2-chelated dipyrromethene (BODIPY), "porphyrin's little sister", have been widely used in constructing these artificial photosynthetic models due to their unique properties. In these photosynthetic models, BODIPYs act as not only excellent antenna molecules, but also as electron-donor and -acceptor molecules in both the covalently linked molecular and supramolecular systems formed by axial coordination, hydrogen bonding, or crown ether complexation. The relationships between the structures and photochemical reactivities of these novel molecular and supramolecular systems are discussed in relation to the efficiency of charge separation and charge recombination. Femto- and nanosecond transient absorption and photoelectrochemical techniques have been employed in these studies to give clear evidence for the occurrence of energy- and electron-transfer reactions and to determine their rates and efficiencies.

Photoinduced electron transfer of zinc porphyrin-oligo(thienylenevinylene)-fullerene[60] triads; thienylenevinylenes as efficient molecular wires.

Two novel donor-bridge-acceptor arrays (ZnP-nTV-C60) with zinc porphyrin (ZnP) and fullerene (C60), covalently connected by oligo(thienylenevinylene) (nTV) molecular wires (n = 3 and 8; ), have been prepared in a multistep convergent manner. The influence of the nTV-length on the electrochemical and electronic properties of the ZnP-nTV-C60 triads has been revealed. Interestingly, an efficient photoinduced electron transfer process occurs in both triads with formation of intermediate radical-ion pairs (namely, ZnP˙(+)-nTV-C60˙(-) and ZnP-nTV˙(+)-C60˙(-)) as confirmed by the nanosecond transient absorption measurements in the visible and NIR regions. In polar and nonpolar solvents, the rate constants of charge-separation processes (kCS) via(1)ZnP*-nTV-C60 were found to decrease from ca. 1.2 × 10(10) s(-1) for n = 3 (RDA = 20 Å) to (5-7) × 10(9) s(-1) for n = 8 (RDA = 60 Å) on the basis of fluorescence lifetime measurements of the ZnP moiety. From these data, together with those previously obtained ones for n = 4 in the related ZnP-nTV-C60 systems, a low attenuation coefficient was evaluated for the nTV molecular wires.

Cellulose acetate nanofiber modified with polydopamine polymerized MOFs for efficient removal of noxious organic dyes.

The need to effectively remove toxic organic dyes from aquatic systems has become an increasingly critical issue in the recent years. In pursuit of this objective, polydopamine (PDA)-binary ZIF-8/UiO-66 (MOFs) was synthesized and incorporated into cellulose acetate (CA), producing ZIF-8/UiO-66/PDA@CA composite nanofibers under meticulously optimized conditions. The potential of fabricated nanofibers to remove cationic methylene blue (MB) dye was investigated. Various analysis tools including FTIR, XRD, SEM, zeta potential, BET, tensile strength testing, and XPS were employed. Results revealed a substantial leap in tensile strength, with ZIF-8/UiO-66/PDA@CA registering an impressive 2.8 MPa, as a marked improvement over the neat CA nanofibers (1.1 MPa). ZIF-8/UiO-66/PDA@CA nanofibers exhibit an outstanding adsorption capacity of 82 mg/g, notably outperforming the 22.4 mg/g capacity of neat CA nanofibers. In binary dye systems, these nanofibers exhibit a striking maximum adsorption capacity of 108 mg/g, establishing their eminence in addressing the complexities of wastewater treatment. Furthermore, the adsorption data fitted to the Langmuir isotherm, and the pseudo-second-order kinetic model. The fabricated nanofiber demonstrates good reproducibility and durability, consistently upholding its performance over five cycles. This suite of remarkable attributes collectively underscores its potential as a robust, durable, and highly promising solution for the effective and efficient removal of pernicious MB dye, in the context of both water quality improvement and environmental preservation.

Tailoring MIL-100(Fe)-derived catalyst for controlled carbon dioxide conversion and product selectivity.

Here in, we are reporting the effect of the catalyst particle size on the catalytic activity and product selectivity by understanding the strength of the interaction between the active catalyst and the reactants (CO2 and H2). In this regard, two catalytic systems having different active catalyst particle sizes and support surface areas were synthesized using metal-organic frameworks (MOF) (MIL-100(Fe)) having two crystal size ranges as sacrificial templates. The active catalyst having smaller nanoparticles exhibited greater chemisorption of hydrogen (Fe-H bond), resulting in heightened selectivity for paraffin due to hydrogenation of re-adsorbed olefins. Conversely, larger nanoparticles showed enhanced chemisorption of CO2 (Fe-C bond), leading to increased selectivity for olefins (O/P = 0.15). Additionally, a reduction in particle size boosts activity from 24% to 38.7% at 340 °C/20 bar. While, higher particle size enhances the selectivity towards C5+ from 11.1 to 45.6% at (300 °C/10 bar) and 9.6 to 21.3% at (340 °C/20 bar).

A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc-porphyrin-fullerene polyad.

A novel multimodular donor-acceptor polyad featuring zinc porphyrin, fullerene, ferrocene, and triphenylamine entities was designed, synthesized, and studied as a charge-stabilizing, photosynthetic-antenna/reaction-center mimic. The ferrocene and fullerene entities, covalently linked to the porphyrin ring, were distantly separated to accomplish the charge-separation/hole-migration events leading to the creation of a long-lived charge-separated state. The geometry and electronic structures of the newly synthesized compound was deduced by B3LYP/3-21G(*) optimization, while the energy levels for different photochemical events was established using data from the optical absorption and emission, and electrochemical studies. Excitation of the triphenylamine entities revealed singlet-singlet energy transfer to the appended zinc porphyrin. As predicted from the energy levels, photoinduced electron transfer from both the singlet and triplet excited states of the zinc porphyrin to fullerene followed by subsequent hole migration involving ferrocene was witnessed from the transient absorption studies. The charge-separated state persisted for about 8.5 µs and was governed by the distance between the final charge-transfer product, that is, a species involving a ferrocenium cation and a fullerene radical anion, with additional influence from the charge-stabilizing triphenylamine entities located on the zinc-porphyrin macrocycle.

Photosynthetic antenna-reaction center mimicry with a covalently linked monostyryl boron-dipyrromethene-aza-boron-dipyrromethene-C60 triad.

An efficient functional mimic of the photosynthetic antenna-reaction center has been designed and synthesized. The model contains a near-infrared-absorbing aza-boron-dipyrromethene (ADP) that is connected to a monostyryl boron-dipyrromethene (BDP) by a click reaction and to a fullerene (C60 ) using the Prato reaction. The intramolecular photoinduced energy and electron-transfer processes of this triad as well as the corresponding dyads BDP-ADP and ADP-C60 have been studied with steady-state and time-resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge-separated states. Such calculations show that electron transfer from the singlet excited ADP ((1) ADP*) to C60 yielding ADP(.+) -C60 (.-) is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from (1) BDP* to ADP in the dyad BDP-ADP and electron transfer from (1) ADP* to C60 in the dyad ADP-C60 . Sequential energy and electron transfer have also been clearly observed in the triad BDP-ADP-C60 . By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10(11)  s(-1) ). The dynamics of electron transfer through (1) ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge-separation process from (1) ADP* to C60 has been detected, which gives the relatively long-lived BDP-ADP(.+) C60 (.-) with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge-separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP-ADP and ADP-C60 , and the triad BDP-ADP-C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.

Excitation-wavelength-dependent, ultrafast photoinduced electron transfer in bisferrocene/BF2-chelated-azadipyrromethene/fullerene tetrads.

Donor-acceptor distance, orientation, and photoexcitation wavelength are key factors in governing the efficiency and mechanism of electron-transfer reactions both in natural and synthetic systems. Although distance and orientation effects have been successfully demonstrated in simple donor-acceptor dyads, revealing excitation-wavelength-dependent photochemical properties demands multimodular, photosynthetic-reaction-center model compounds. Here, we successfully demonstrate donor- acceptor excitation-wavelength-dependent, ultrafast charge separation and charge recombination in newly synthesized, novel tetrads featuring bisferrocene, BF2 -chelated azadipyrromethene, and fullerene entities. The tetrads synthesized using multistep synthetic procedure revealed characteristic optical, redox, and photo reactivities of the individual components and featured "closely" and "distantly" positioned donor-acceptor systems. The near-IR-emitting BF2-chelated azadipyrromethene acted as a photosensitizing electron acceptor along with fullerene, while the ferrocene entities acted as electron donors. Both tetrads revealed excitation-wavelength-dependent, photoinduced, electron-transfer events as probed by femtosecond transient absorption spectroscopy. That is, formation of the Fc(+)-ADP-C60(.-) charge-separated state upon C60 excitation, and Fc(+)-ADP(.-)-C60 formation upon ADP excitation is demonstrated.