A Supramolecular Tetrad Featuring Covalently Linked Ferrocene–Zinc Porphyrin–BODIPY Coordinated to Fullerene: A Charge Stabilizing,Photosynthetic Antenna–Reaction Center Mimic

A novel photosynthetic‐antenna–reaction‐center model compound, comprised of BF₂‐chelated dipyrromethene (BODIPY) as an energy‐harvesting antenna, zinc porphyrin (ZnP) as the primary electron donor, ferrocene (Fc) as a hole‐shifting agent, and phenylimidazole‐functionalized fulleropyrrolidine (C₆₀Im) as an electron acceptor, has been synthesized and characterized. Optical absorption and emission, computational structure optimization, and cyclic voltammetry studies were systematically performed to establish the role of each entity in the multistep photochemical reactions. The energy‐level diagram established from optical and redox data helped identifying different photochemical events. Selective excitation of BODIPY resulted in efficient singlet energy transfer to the ZnP entity. Ultrafast electron transfer from the ¹ZnP* (formed either as a result of singlet–singlet energy transfer or direct excitation) or ¹C₆₀* of the coordinated fullerene resulting into the formation of the Fc–(C₆₀ ^{. ?}Im:ZnP ^{. +})–BODIPY radical ion pair was witnessed by femtosecond transient absorption studies. Subsequent hole migration to the ferrocene entity resulted in the Fc⁺–(C₆₀ ^{. +}Im:ZnP)–BODIPY radical ion pair that persisted for 7–15 μs, depending upon the solvent conditions and contributions from the triplet excited states of ZnP and ImC₆₀, as revealed by the nanosecond transient spectral studies. Better utilization of light energy in generating the long‐lived charge‐separated state with the help of the present “antenna–reaction‐center” model system has been successfully demonstrated.     

Stabilization of the Charge‐Separated States of Covalently Linked Zinc Porphyrin–Triphenylamine–[60]Fullerene

Spectroscopic, redox, computational, and electron transfer reactions of the covalently linked zinc porphyrin–triphenylamine–fulleropyrrolidine system are investigated in solvents of varying polarity. An appreciable interaction between triphenylamine and the porphyrin π system is revealed by steady‐state absorption and emission, redox, and computational studies. Free‐energy calculations suggest that the light‐induced processes via the singlet‐excited porphyrin are exothermic in benzonitrile, dichlorobenzene, toluene, and benzene. The occurrence of fast and efficient charge‐separation processes (≈10¹² s^?1) via the singlet‐excited porphyrin is confirmed by femtosecond transient absorption measurements in solvents with dielectric constants ranging from 25.2 (benzonitrile) to 2.2 (benzene). The rates of the charge separation processes are much less solvent‐dependent, which suggests that the charge‐separation processes occur at the top region of the Marcus parabola. The lifetimes of the singlet radical‐ion pair (70–3000 ps at room temperature) decrease substantially in more polar solvents, which suggests that the charge‐recombination process is occurring in the Marcus inverted region. Interestingly, by utilizing the nanosecond transient absorption spectral technique we can obtain clear evidence about the existence of triplet radical‐ion pairs with relatively long lifetimes of 0.71 μs (in benzonitrile) and 2.2 μs (in o‐dichlorobenzene), but not in toluene and benzene due to energetic considerations. From the point of view of mechanistic information, the synthesized zinc porphyrin–triphenylamine–fulleropyrrolidine system has the advantage that both the lifetimes of the singlet and triplet radical‐ion pair can be determined.     

Multistep Energy and Electron Transfer in a “V‐Configured” Supramolecular BODIPY–azaBODIPY–Fullerene Triad: Mimicry of Photosynthetic Antenna Reaction‐Center Events

A new photosynthetic antenna‐reaction‐center model compound composed of covalently linked BF₂‐chelated dipyrromethene (BODIPY), BF₂‐chelated azadipyrromethene (azaBODIPY), and fullerene (C₆₀), in a “V‐configuration”, has been newly synthesized and characterized by using a multistep synthetic procedure. Optical absorbance and steady‐state fluorescence, computational, and electrochemical studies were systematically performed in nonpolar, toluene, and polar, benzonitrile, solvents to establish the molecular integrity of the triad and to construct an energy‐level diagram revealing different photochemical events. The geometry obtained by B3LYP/6‐31G* calculations revealed the anticipated V‐configuration of the BODIPY‐azaBODIPY‐C₆₀ triad. The location of the frontier orbitals in the triad tracked the site of electron transfer determined from electrochemical studies. The different photochemical events originated from ¹BODIPY* were realized from the energy‐level diagram. Accordingly, ¹BODIPY* resulted in competitive ultrafast energy transfer to produce BODIPY–¹azaBODIPY*–C₆₀ and electron transfer to produce BODIPY ^{. +}–azaBODIPY–C₆₀ ^{. ?} as major photochemical events. The charge‐separated state persisted for few nanoseconds prior populating ³C₆₀*, which in turn revealed an unusual triplet–triplet energy transfer to produce ³azaBODIPY* prior returning to the ground state. These findings delineate the importance of multimodular systems in energy harvesting, and more importantly, their utility in building multifunction performing optoelectronic devices.     

Ultrafast Photoinduced Charge Separation in Wide‐Band‐Capturing Self‐Assembled Supramolecular Bis(donor styryl)BODIPY–Fullerene Conjugates

A new series of self‐assembled supramolecular donor–acceptor conjugates capable of wide‐band capture, and exhibiting photoinduced charge separation have been designed, synthesized and characterized using various techniques as artificial photosynthetic mimics. The donor host systems comprise of a 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) containing a crown ether entity at the meso‐position and two styryl entities on the pyrrole rings. The styryl end groups also carried additional donor (triphenylamine or phenothiazine) entities. The acceptor host system was a fulleropyrrolidine comprised of an ethylammonium cation. Owing to the presence of extended conjugation and multiple chromophore entities, the BODIPY host revealed absorbance and emission well into the near‐IR region covering the 300–850 nm spectral range. The donor–acceptor conjugates formed by crown ether–alkyl ammonium cation binding of the host–guest system was characterized by optical absorbance and emission, computational, and electrochemical techniques. Experimentally determined binding constants were in the range of 1–2×10⁵ M ^?1. An energy‐level diagram to visualize different photochemical events was established using redox, computational, absorbance, and emission data. Spectral evidence for the occurrence of photoinduced charge separation in these conjugates was established from femtosecond transient absorption studies. The measured rates indicated ultrafast charge separation and relatively slow charge recombination revealing their usefulness in light‐energy harvesting and optoelectronic device applications. The bis(donor styryl)BODIPY‐derived conjugates populated their triplet excited states during charge recombination.     

Supramolecular Formation of Li+@PCBM Fullerene with Sulfonated Porphyrins and Long‐Lived Charge Separation

Lithium‐ion‐encapsulated [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester fullerene (Li⁺@PCBM) was utilized to construct supramolecules with sulfonated meso‐tetraphenylporphyrins (MTPPS^4?; M=Zn, H₂) in polar benzonitrile. The association constants were determined to be 1.8×10⁵ M ^?1 for ZnTPPS^4?/Li⁺@PCBM and 6.2×10⁴ M ^?1 for H₂TPPS^4?/Li⁺@PCBM. From the electrochemical analyses, the energies of the charge‐separated (CS) states were estimated to be 0.69 eV for ZnTPPS^4?/Li⁺@PCBM and 1.00 eV for H₂TPPS^4?/Li⁺@PCBM. Upon photoexcitation of the porphyrin moieties of MTPPS^4?/Li⁺@PCBM, photoinduced electron transfer occurred to produce the CS states. The lifetimes of the CS states were 560 μs for ZnTPPS^4?/Li⁺@PCBM and 450 μs for H₂TPPS^4?/Li⁺@PCBM. The spin states of the CS states were determined to be triplet by electron paramagnetic resonance spectroscopy measurements at 4 K. The reorganization energies (λ) and electronic coupling term (V) for back electron transfer (BET) were determined from the temperature dependence of k_BET to be λ=0.36 eV and V=8.5×10^?3 cm^?1 for ZnTPPS^4?/Li⁺@PCBM and λ=0.62 eV and V=7.9×10^?3 cm^?1 for H₂TPPS^4?/Li⁺@PCBM based on the Marcus theory of nonadiabatic electron transfer. Such small V values are the result of a small orbital interaction between the MTPPS^4? and Li⁺@PCBM moieties. These small V values and spin‐forbidden charge recombination afford a long‐lived CS state.     

Photoinduced Energy and Electron Transfer in Phenylethynyl‐Bridged Zinc Porphyrin–Oligothienylenevinylene–C60 Ensembles

Donor–bridge–acceptor triad (Por‐2TV‐C₆₀) and tetrad molecules ((Por)₂‐2TV‐C₆₀), which incorporated C₆₀ and one or two porphyrin molecules that were covalently linked through a phenylethynyl‐oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto‐ and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C₆₀ moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C₆₀ moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C₆₀. Then, back‐electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)‐2TV‐C₆₀ and (Por)₂‐2TV‐C₆₀ acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C₆₀.     

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.     

A Synthetic Chlorophyll Dimer Appending Fullerene: Effect of Chlorophyll Pairing on (Photo)redox Properties

Accurately mimicking structure and function of natural chlorophyll (Chl) assemblies is very challenging. Herein, we report the synthesis of a fullerene-appended Chl dimer being capable of intramolecular photoinduced charge separation (CS) with a unique structure reminiscent of reaction centers (RCs) in phototrophs. Structural analyses revealed that the Chl dimer adopts a bird-like structure in which two Chl components overlapped partially with one of the four pyrrole rings in a Chl ring similar to in a Chl pair in the natural RC complexes. A comparative study including voltammetry and spectrometric analyses using the Chl dimer and its corresponding monomer with and without a fullerene moiety was performed to gain insight into the effect of Chl pairing on (photo)redox properties. Our results suggest that the present dimer motif that closely resemble the Chl pair in natural RCs lead to more facile oxidation and lower energy of the CS state of the Chl dimer than those of the Chl monomer, resulting in its photoredox behavior different from that of the monomer Chl.     

A Supramolecular Photosynthetic Model Made of a Multiporphyrinic Array Constructed around a C60 Core and a C60–Imidazole Derivative

The photophysical properties of a supramolecular fullerene–porphyrin ensemble resulting from the self‐assembly of a pyrrolidinofullerene–imidazole derivative ( F1 ) with a multimetalloporphyrin array constructed around a hexasubstituted fullerene core ( F(ZnP)₁₂ ) have been investigated. The fullerene hexa‐adduct core of the host system does not play any active role in the cascade of photoinduced events of the supramolecular ensemble, indeed no intercomponent photoinduced processes could be observed in host F(ZnP)₁₂ . In contrast, upon axial coordination with the monosubstituted fullerene guest F1 , a quantitative quenching of the fluorescence signal of the metalloporphyrins was observed for the supramolecular complex [F(ZnP)₁₂(F1) _n ] both in polar and nonpolar solvents. In toluene, the supramolecular ensemble exhibits a charge transfer emission centered around 930 nm, suggesting the occurrence of intramolecular face‐to‐face interactions of F1 with neighboring metalloporphyrin moieties within the self‐assembled photoactive array. This mechanism is supported by the fact that a one order of magnitude increase in the binding constant was observed for the supramolecular complex [F(ZnP)₁₂(F1) _n ] when compared with a reference system lacking the pyrrolidinofullerene unit. In benzonitrile, a long‐lived charge‐separated state (τ=0.3 μs) has been detected for the supramolecular adduct.     

Phenothiazine–BODIPY–Fullerene Triads as Photosynthetic Reaction Center Models: Substitution and Solvent Polarity Effects on Photoinduced Charge Separation and Recombination

Novel photosynthetic reaction center model compounds of the type donor₂–donor₁–acceptor, composed of phenothiazine, BF₂‐chelated dipyrromethene (BODIPY), and fullerene, respectively, have been newly synthesized using multistep synthetic methods. X‐ray structures of three of the phenothiazine‐BODIPY intermediate compounds have been solved to visualize the substitution effect caused by the phenothiazine on the BODIPY macrocycle. Optical absorption and emission, computational, and differential pulse voltammetry studies were systematically performed to establish the molecular integrity of the triads. The N‐substituted phenothiazine was found to be easier to oxidize by 60 mV compared to the C‐substituted analogue. The geometry and electronic structures were obtained by B3LYP/6‐31G(dp) calculations (for H, B, N, and O) and B3LYP/6‐31G(df) calculations (for S) in vacuum, followed by a single‐point calculation in benzonitrile utilizing the polarizable continuum model (PCM). The HOMO?1, HOMO, and LUMO were, respectively, on the BODIPY, phenothiazine and fullerene entities, which agreed well with the site of electron transfer determined from electrochemical studies. The energy‐level diagram deduced from these data helped in elucidating the mechanistic details of the photochemical events. Excitation of BODIPY resulted in ultrafast electron transfer to produce PTZ–BODIPY^.+–C₆₀^.?; subsequent hole shift resulted in PTZ^.+–BODIPY–C₆₀^.? charge‐separated species. The return of the charge‐separated species was found to be solvent dependent. In nonpolar solvents the PTZ^.+–BODIPY–C₆₀^.? species populated the ³C₆₀* prior to returning to the ground state, while in polar solvent no such process was observed due to relative positioning of the energy levels. The ¹BODIPY* generated radical ion‐pair in these triads persisted for few nanoseconds due to electron transfer/hole‐shift mechanism.     

Charge Separation in Graphene‐Decorated Multimodular Tris(pyrene)–Subphthalocyanine–Fullerene Donor–Acceptor Hybrids

A new approach to probe the effect of graphene on photochemical charge separation in donor–acceptor conjugates is devised. For this, multimodular donor–acceptor conjugates, composed of three molecules of pyrene, a subphthalocyanine, and a fullerene C₆₀ ((Pyr)₃SubPc‐C₆₀), have been synthesized and characterized. These systems were hybridized on few‐layer graphene through π–π stacking interactions of the three pyrene moieties. The hybrids were characterized using Raman, HRTEM, and spectroscopic and electrochemical techniques. The energy levels of the donor–acceptor conjugates were fine‐tuned upon interaction with graphene and photoinduced charge separation in the absence and presence of graphene was studied by femtosecond transient absorption spectroscopy. Accelerated charge separation and recombination was detected in these graphene‐decorated conjugates suggesting that they could be used as materials for fast‐responding optoelectronic devices and in light energy harvesting applications.     

Supramolecular Architectures by Fullerene‐Bridged Bis(permethyl‐β‐cyclodextrin)s with Porphyrins

The Hirsch–Bingel reaction of bis{4‐methyl[1,2,3]triazolyl}malonic ester‐bridged bis(permethyl‐β‐cyclodextrin) 1 with C₆₀ has led to the formation of a new fullerene‐bridged bis(permethyl‐β‐cyclodextrin) 2 , which has been comprehensively characterized by NMR spectroscopy, MALDI‐MS, and elemental analysis. Taking advantage of the high affinity between 2 and 5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphyrin ( 3 ) or [5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphinato]zinc(II) ( 4 ), linear supramolecular architectures with a width of about 2 nm and a length ranging from hundreds of nanometers to micron dimension were conveniently constructed and fully investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Significantly, the photoinduced electron‐transfer (PET) process between porphyrin and C₆₀ moieties takes place within the 2 ? 3 and 2 ? 4 supramolecular architectures under light irradiation, leading to the highly efficient quenching of the porphyrin fluorescence. The PET process and the charge‐separated state were investigated by means of fluorescence spectroscopy, fluorescence decay, cyclic voltammetry, and nanosecond transient absorption measurements.     

Covalently Linked Bis(Amido-Corroles): Inter- and Intramolecular Hydrogen-Bond-Driven Supramolecular Assembly

Four bis-corroles linked by diamide bridges were synthesized through peptide-type coupling of a trans-A₂B-corrole acid with aliphatic and aromatic diamines. In the solid state, the hydrogen-bond pattern in these bis-corroles is strongly affected by the type of solvent used in the crystallization process. Although intramolecular hydrogen bonds play a decisive role, they are supported by intermolecular hydrogen bonds and weak N−H⋅⋅⋅π interactions between molecules of toluene and the corrole cores. In an analogy to mono(amido-corroles), both in crystalline state and in solutions, the aliphatic or aromatic bridge is located directly above the corrole ring. When either ethylenediamine or 2,3-diaminonaphthalene are used as linkers, incorporation of polar solvents into the crystalline lattice causes a roughly parallel orientation of the corrole rings. At the same time, both NHCO⋅⋅⋅NH corrole hydrogen bonds are intramolecular. In contrast, solvation in toluene causes a distortion with one of the hydrogen bonds being intermolecular. Interestingly, intramolecular hydrogen bonds are always formed between the –NHCO– functionality located further from the benzene ring present at the position 10-meso. In solution, the hydrogen-bonds pattern of the bis(amido-corroles) is strongly affected by the type of the solvent. Compared with toluene (strongly high-field shifted signals), DMSO and pyridine disrupt self-assembly, whereas hexafluoroisopropanol strengthens intramolecular hydrogen bonds.     

Mono‐ and Bis(tetrathiafulvalene)‐1,3,5‐Triazines as Covalently Linked Donor–Acceptor Systems: Structural,Spectroscopic, and Theoretical Investigations

Reaction of 2,4,6‐trichloro‐1,3,5‐triazine with lithiated tetrathiafulvalene (TTF) in stoichiometric conditions, followed by treatment with sodium methanolate, provides mono‐ and bis(TTF)–triazines as new covalently linked (multi)donor–acceptor systems. Single‐crystal X‐ray analyses reveal planar structures for both compounds, with formation of peculiar segregated donor and acceptor stacks for the mono(TTF)–triazine compound, while mixed TTF–triazine stacks establish in the case of the bis(TTF) derivative. Cyclic voltammetry measurements show reversible oxidation of the TTF units, at rather low potential, with no splitting of the oxidation waves in the case of the dimeric TTF, whereas irreversible reduction of the triazine core is observed. Intramolecular charge transfer is experimentally evidenced through solution electronic absorption spectroscopy. Time‐dependent DFT calculations allow the assignment of the charge transfer band to singlet transitions from the HOMO of the donor(s) to the LUMO of the acceptor. Solution EPR measurements correlated with theoretical calculations were performed in order to characterize the oxidized species. In both cases the spectra show very stable radical species and contain a triplet of doublet pattern, in agreement with the coupling of the unpaired electron with the three TTF protons. The dication of the bis(TTF)–triazine is paramagnetic, but no spin–spin exchange interaction could be detected.     

Studies on Intra‐Supramolecular and Intermolecular Electron‐Transfer Processes between Zinc Naphthalocyanine and Imidazole‐Appended Fullerene

Spectroscopic, computational, redox, and photochemical behavior of a self‐assembled donor‐acceptor dyad formed by axial coordination of zinc naphthalocyanine, ZnNc, and fulleropyrrolidine bearing an imidazole coordinating ligand (2‐(4′‐imidazolylphenyl)fulleropyrrolidine, C₆₀Im) was investigated in noncoordinating solvents, toluene and o‐dichlorobenzene, and the results were compared to the intermolecular electron transfer processes in a coordinating solvent, benzonitrile. The optical absorption and ab initio B3 LYP/3–21G(*) computational studies revealed self‐assembled supramolecular 1:1 dyad formation between the ZnNc and C₆₀Im entities. In the optimized structure, the HOMO was found to be entirely located on the ZnNc entity while the LUMO was found to be entirely on the fullerene entity. Cyclic voltammetry studies of the dyad exhibited a total of seven one‐electron redox processes in o‐dichlorobenzene, with 0.1 M tetrabutylammonium perchlorate. The excited‐state electron‐transfer processes were monitored by both optical‐emission and transient‐absorption techniques. Direct evidence for the radical‐ion‐pair (C₆₀Im^.?:ZnNc ^{. +} ) formation was obtained from picosecond transient‐absorption spectral studies, which indicated charge separation from the singlet‐excited ZnNc to the C₆₀Im moiety. The calculated rates of charge separation and charge recombination were 1.4×10¹⁰ s^?1 and 5.3×10⁷ s^?1 in toluene and 8.9×10⁹ s^?1 and 9.2×10⁷ s^?1 in o‐dichlorobenzene, respectively. In benzonitrile, intermolecular electron transfer from the excited triplet state of ZnNc to C₆₀Im occurs and the second‐order rate constant (k_q^triplet) for this quenching process was 5.3×10⁸ M ^?1 s^?1.     

High‐Potential Perfluorinated Phthalocyanine–Fullerene Dyads for Generation of High‐Energy Charge‐Separated States: Formation and Photoinduced Electron‐Transfer Studies

High oxidation potential perfluorinated zinc phthalocyanines (ZnF_nPcs) are synthesised and their spectroscopic, redox, and light‐induced electron‐transfer properties investigated systematically by forming donor–acceptor dyads through metal–ligand axial coordination of fullerene (C₆₀) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine‐ (Py) and phenylimidazole‐functionalised fullerene (C₆₀Im) derivatives to the zinc centre of the F_nPcs. The determined binding constants, K, in o‐dichlorobenzene for the 1:1 complexes are in the order of 10⁴ to 10⁵ M ^?1; nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6‐31G* method. The HOMO and LUMO levels are located on the Pc and C₆₀ entities, respectively; this suggests the formation of ZnF_nPc^.+–C₆₀Im^.? and ZnF_nPc^.+–C₆₀Py^.? (n=0, 8 or 16) intra‐supramolecular charge‐separated states during electron transfer. Electrochemical studies on the ZnPc–C₆₀ dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge‐separated states. The energy of the charge‐separated state for dyads composed of ZnF_nPc is higher than that of normal ZnPc–C₆₀ dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar‐energy harvesting and optoelectronic device building applications.