Metal-ligand Axial Coordination Research Articles

Zinc Tetrapyrrole Coordinated to Imidazole Functionalized Tetracyanobutadiene or Cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene Conjugates: Dark vs. Light-Induced Electron Transfer.

Using the popular metal-ligand axial coordination self-assembly approach, donor-acceptor conjugates have been constructed using zinc tetrapyrroles (porphyrin (ZnP), phthalocyanine (ZnPc), and naphthalocyanine (ZnNc)) as electron donors and imidazole functionalized tetracyanobutadiene (Im-TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene (Im-DCNQ) as electron acceptors. The newly formed donor-acceptor conjugates were fully characterized by a suite of physicochemical methods, including absorption and emission, electrochemistry, and computational methods. The measured binding constants for the 1 : 1 complexes were in the order of 104 -105 M-1 in o-dichlorobenzene. Free-energy calculations and the energy level diagrams revealed the high exergonicity for the excited state electron transfer reactions. However, in the case of the ZnNc:Im-DCNQ complex, owing to the facile oxidation of ZnNc and facile reduction of Im-DCNQ, slow electron transfer was witnessed in the dark without the aid of light. Systematic transient pump-probe studies were performed to secure evidence of excited state charge separation and gather their kinetic parameters. The rate of charge separation was as high as 1011 s-1 suggesting efficient processes. These findings show that the present self-assembly approach could be utilized to build donor-acceptor constructs with powerful electron acceptors, TCBD and DCNQ, to witness ground and excited state charge transfer, fundamental events required in energy harvesting, and building optoelectronic devices.

(Nanocarbons Division Robert C. Haddon Research Award) Nano Carbons in Mimicking the Early Events of Photosynthetic Reaction Center: ‘Simple’ and ‘Not-so-Simple’ Donor-Acceptor Conjugates

Light-induced electron transfer is a key step in solar energy conversion, and a process with myriad relevance in the fields of artificial photosynthesis, photocatalysis, photoconductivity, and photovoltaics. In a donor-acceptor, D-A system, light absorption by a chromophore results in the formation of an excited state species, followed by a charge transfer between an electron donor (D) and an electron acceptor (A) leading to a charge-separated D .+ -A .- species.The optimization of these processes and comprehending their mutual interplay to ultimately achieve charge-separated species is of paramount importance for the development of efficient systems in solar light conversion schemes.The present talk summarizes our research over the years focused on utilizing nano carbons, viz., fullerenes, endohedral fullerenes, carbon nanotubes, and graphene in the construction of donor-acceptor systems capable of undergoing photoinduced energy and electron transfer events. Both, covalently linked with rigid, semi-rigid, flexible, or conjugated spacers, and self-assembled via metal-ligand axial coordination, ion-pairing, ion-dipole, or hydrogen bonding strategies were utilized in the construction of donor-acceptor conjugates. Multi-modular donor-acceptor constructs were designed, synthesized, and studied to probe sequential energy and electron transfer events, finally resulting in long-lived charge-separated states. In some instances, these molecular systems were also used as photocatalytic energy conversion schemes. The pros and cons of utilizing nanocarbon materials as photo-active functional materials will be highlighted. D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ Phys. Chem. Letts. 2010, 1. 2586-2593.D’Souza, and O. Ito ‘Photosensitized electron transfer processes of nano carbons applicable to solar cells,’ Chem. Soc. Rev. 2012, 41, 86-96.B. KC, F. D’Souza, ‘Design and photochemical study of supramolecular donor-acceptor systems assembled via metal-ligand axial coordination Coord. Chem. Rev. 2016, 322, 104-141.Bottari, M. A. Herranz, L. Wibmer, M. Vollard, L. Rodriguez-Perez, D. M. Guldi, A. Hirsch, N. Martin, F. D’Souza, T. Torres, Chemical functionalization and characterization of graphene-based materials, Chem. Soc. Rev. 2017, 46, 4464-4500.Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992.Kazemi, Y. Jang, A. Liyanage, P. A. Karr, and F. D’Souza, ‘A Carbon Nanotube Binding Bis(pyrenylstyryl)BODIPY-C60 Nano Tweezer: Charge Stabilization through Sequential Electron Transfer’, Angew. Chem. Int. Ed. 2022, in press

Highly Coupled Heterobicycle-Fused Porphyrin Dimers: Excitonic Coupling and Charge Separation with Coordinated Fullerene, C60.

Porphyrin dimers have been widely explored and studied owing to their importance in photosynthetic systems. A vast variety of dimers linked by different groups and at different angles have been synthesized and studied; however, the means by which to synthesize rigidly fused porphyrins with direct conjugation of the chromophores remains limited. Such a class of porphyrins may possess interesting properties that unconjugated or stacked dimers may not exhibit. In this study, bisbenzimidazole-fused porphyrin dimers and their mono- and bis-zinc derivatives are synthesized and characterized. As a consequence of excitonic coupling, these dimers exhibit a split Soret band irrespective of the metal ion in the porphyrin cavity. Steady-state fluorescence and excitation spectra followed by femtosecond transient absorption spectral studies of the heterometallated dimer, (free-base and zinc porphyrin) reveals the occurrence of efficient singlet-singlet energy transfer (>95 % efficiency and rate constant >1012 s-1 ) within the dyad. Further, donor-acceptor conjugates were formed by metal-ligand axial coordination of phenyl imidazole functionalized C60 and were characterized by a variety of physicochemical techniques. Excited state charge separation from both singlet and triplet excited states of ZnP in the conjugates has been established. The lifetime of the final charge-separated state was in the 30-40 μs range revealing charge stabilization. Interestingly, no charge separation in the conjugate derived from the heterometallated dimer was observed wherein excitation transfer dominated the process. The present study brings out the importance of the rigid π-spacer connecting porphyrin dimers in governing the energy and electron transfer events when coupled with an electron acceptor.

Solid-state supramolecular structures and excellent photothermal activities of dimeric zinc(II) phthalocyanines axially bridged with bipyridine derivatives

Metal-ligand axial coordination of zinc(II) phthalocyanines is an efficient strategy for regulation of structures and properties. In this work, we designed and prepared four unsubstituted zinc(II) phthalocyanine (ZnPc) dimer-based supramolecular complexes (1–4) via axtial coordination with bipyridine derivatives. Single crystal X-ray analysis revealed that the four novel complexes were dimeric (i.e. ZnPc-ligand-ZnPc), with H-shape for 1, saddle-like for 2, and Z-shapes for 3 and 4. It's interesting that a pair of saddle-like dimers of 2 crossed each other to form an interlocked tetramer structure. Furthermore, 3 and 4 were dense stacking because of their semirigid ligands, which significantly enhanced the intermolecular interactions. Intriguingly, in the crystal structure of 4, the naphthalimide ring of the ligand embedded into two neighboring phthalocyanine macrocycles, resulting in a slipped sandwich structure of ZnPc-naphthalimide-ZnPc with double π···π interactions. More importantly, the strong intermolecular interactions led to very broad absorption spectra in vis-NIR region, quenched fluorescence, and highly efficient photothermal effect. Upon irradiation, 3 and 4 could reach up to 85.7 °C and 89.2 °C, respectively, enabling them to serve as outstanding photothermal conversion materials used for photothermal imaging and therapy.

Double-layer novel zinc porphyrin based on axial coordination self-assembly for dye-sensitized solar cells

Porphyrin sensitizers have attracted great attention due to their admirable performance in dye-sensitized solar cell (DSSC). In this work, three antenna zinc porphyrins ZnPi (i = 1–3) and anchored porphyrin ZnPA have been designed, synthesized, and characterized. The antenna molecules ZnPi adhere on to the anchored porphyrin ZnPA via metal–ligand axial coordination self-assembly, and then the ZnPA bonding to nanostructured TiO2 to prepared ZnPi(i = 1–3)-ZnPA based DSSCs. Optical performance analysis showed that the devices based on self-assemblies exhibited obviously enhanced light-harvesting ability than the monomer anchor molecule ZnPA. The photovoltaic results showed that, compared with the ZnPA-sensitized solar cell, the ZnPi(i = 1–3)-ZnPA-sensitized solar cells have higher short - circuit photocurrent density (Jsc). However, the open circuit voltage (Voc) of the self-assembled porphyrin-sensitized solar cells are lower than the ZnPA-sensitized solar cell, this is because of the increase of charge recombination rate of the self-assembled porphyrin-sensitized solar cells on the electrode. As a result, the devices based ZnPi (i = 1–3)-ZnPA exhibited enhanced photoelectric conversion efficiency (PCE) than monomer ZnPA-sensitized solar cell. Especially for the ZnP3-ZnPA-sensitized solar cell with a optimal PCE is 3.44%, indicating that the trifluoromethyl substituent of the antenna molecule ZnP3 porphyrin was a more suitable group. Additionally, density functional theory (DFT) calculations are used to further verify the test results of the assembled sensitized solar cells. Therefore, our new method, metal-ligand self-assembly strategy provides new ideas for the high-performance DSSC.

Donor-acceptor conjugates derived from cobalt porphyrin and fullerene via metal-ligand axial coordination: Formation and excited state charge separation

Two types of cobalt porphyrins, viz., meso-tetrakis(tolylporphyrinato)cobalt(II), (TTP)Co (1), and meso-tetrakis(triphenylamino porphyrinato)cobalt(II), [(TPA)4P]Co, (2) were self-assembled via metal-ligand axial coordination of phenyl imidazole functionalized fulleropyrrolidine, ImC[Formula: see text] to form a new series of donor–acceptor constructs. A 1:2 complex formation with ImC[Formula: see text] was established in the case of (TTP)Co while for [(TPA)4P]Co only a 1:1 complex was possible to positively identify. The binding constants [Formula: see text] and [Formula: see text] for step-wise addition of ImC[Formula: see text] to (TTP)Co were found to be 1.07 × 105 and 3.20 × 104 M[Formula: see text], respectively. For [(TPA)4P]Co:ImC[Formula: see text], the measured [Formula: see text] values was found to be 6.48 × 104 M[Formula: see text], slightly smaller than that observed for (TTP)Co. Although both cobalt porphyrins were non-fluorescent, they were able to quench the fluorescence of ImC[Formula: see text] indicating occurrence of excited state events in the supramolecular donor-acceptor complexes. Electrochemistry coupled with spectroelectrochemistry, revealed the formation of cobalt(III) porphyrin cation instead of a cobalt(II) porphyrin radical cation, as the main product, during oxidation of phenyl imidazole coordinated cobalt porphyrin. With the help of computational and electrochemical results, an energy level diagram was constructed to witness excited state photo-events. Competitive energy and electron transfer from excited CoP to coordinated ImC[Formula: see text], and electron transfer from Im1C[Formula: see text]* to cobalt(II) porphyrin resulting into the formation of PCo[Formula: see text]:ImC[Formula: see text] charge separated state was possible to envision from the energy diagram. Finally, using femtosecond transient absorption spectroscopy and data analysis by Glotaran, it was possible to establish sequential occurrence of energy transfer and charge separation processes. The lifetime of the final charge separated state was [Formula: see text] 2 ns. A slightly better charge stabilization was observed in the case of [(TPA)4P]Co:ImC[Formula: see text] due to the presence of electron rich, peripheral triphenylamine substituents on the cobalt porphyrin.

Sequential, Ultrafast Energy Transfer and Electron Transfer in a Fused Zinc Phthalocyanine-free-base Porphyrin-C60 Supramolecular Triad.

A supramolecular triad composed of a fused zinc phthalocyanine-free-base porphyrin dyad (ZnPc-H2 P) coordinated to phenylimidazole functionalized C60 via metal-ligand axial coordination was assembled, as a photosynthetic antenna-reaction centre mimic. The process of self-assembly resulting into the formation of C60 Im:ZnPc-H2 P supramolecular triad was probed by proton NMR, UV-Visible and fluorescence experiments at ambient temperature. The geometry and electronic structures were deduced from DFT calculations performed at the B3LYP/6-31G(dp) level. Electrochemical studies revealed ZnPc to be a better electron donor compared to H2 P, and C60 to be the terminal electron acceptor. Fluorescence studies of the ZnPc-H2 P dyad revealed excitation energy transfer from 1 H2 P* to ZnPc within the fused dyad and was confirmed by femtosecond transient absorption studies. Similar to that reported earlier for the fused ZnPc-ZnP dyad, the energy transfer rate constant, kENT was in the order of 1012 s-1 in the ZnPc-H2 P dyad indicating an efficient process as a consequence of direct fusion of the two π-systems. In the presence of C60 Im bound to ZnPc, photoinduced electron transfer leading to H2 P-ZnPc.+ :ImC60.- charge separated state was observed either by selective excitation of ZnPc or H2 P. The latter excitation involved an energy transfer followed by electron transfer mechanism. Nanosecond transient absorption studies revealed that the lifetime of charge separated state persists for about 120 ns indicating charge stabilization in the triad.

Investigation of the push–pull effects on β-functionalized zinc porphyrin coordinated to C60 donor–acceptor conjugates

Two novel β-functionalized push–pull zinc porphyrins with amine or phenyl push-groups and cyclic imide or carboxylic esters pull-groups have been newly synthesized for light energy harvesting applications. The ethynylphenyl spacers extended the conjugation of the porphyrin π-systems, as reflected by their red-shifted absorbance and fluorescence spectra. Computational studies performed at the B3LYP/6-31G* level indicated no steric hindrance between the porphyrin π-system and the substituents. The calculated HOMO and LUMO orbitals displayed significant delocalization in 1, where the electron density in the HOMO was localized over the push groups, whereas the LUMO was extended over the porphyrin π- and pull-groups. On the other hand, 2 did not display significant orbital segregation, which is attributed to its weaker push–pull character. Electrochemical studies revealed smaller HOMO–LUMO gaps for the push–pull zinc porphyrins. As a consequence of the push–pull effects, reduction in fluorescence intensity and lifetime was observed. Femtosecond transient absorption spectral studies revealed successful formation of singlet excited state in both of the push–pull porphyrins. Donor–acceptor conjugates were subsequently built and characterized by coordinating an electron acceptor, C60Im, via metal–ligand axial coordination. Efficient photo-induced charge separation in both donor–acceptor conjugates was witnessed wherein the charge-separated states persisted tens of nanoseconds prior returning to the ground state.

Charge Stabilization in High-Potential Zinc Porphyrin-Fullerene via Axial Ligation of Tetrathiafulvalene

Extending the lifetime of the charge-separated states generated during photoinduced electron transfer in a covalently linked high-potential zinc porphyrin-fullerene dyad, (F15P)Zn–C60, was accomplished by metal–ligand axial coordination of pyridine-functionalized tetrathiafulvalene (TTF) via a dual-electron-transfer/hole migration mechanism. The meso-aryl positions of the zinc porphyrin carried three penta-fluorophenyl substituents that made the zinc porphyrin ring harder to oxidize by 0.43 V compared with zinc porphyrin with meso-phenyl substituents. Two TTF derivatives, a first with a pyridine directly linked to TTF (Py-TTF) and a second with a phenyl spacer between the pyridine and TTF (Py-phTTF), were employed to vary the distance between the primary photosensitizer/electron donor, zinc porphyrin, and the secondary electron donor, TTF. Both Py-TTF and Py-phTTF coordinated via the pyridine entity to the Zn center with 1:1 molecular stoichiometry and moderate binding constants. The supramolecular triads were characterized by optical absorption and emission, electrochemistry, and computational studies. An energy-level diagram was established to realize the different photochemical events in the triads. Using femtosecond transient absorption spectroscopy, it was possible to show that the coordinated TTF participated in electron transfer from the 1(F15P)Zn* in the case of the C60-(F15P)Zn:TTF triads to produce C60-(F15P)Zn•-:TTF•+ charge-separated state competitively with the electron transfer from the 1(F15P)Zn* to covalently linked C60 to produce C60•--(F15P)Zn•+:TTF charge-separated state. The two charge-separated states, C60-(F15P)Zn•-:TTF•+ and C60•--(F15P)Zn•+:TTF, were further involved in electron migration in the former case and hole transfer in the latter case to produce the C60•--(F15P)Zn:TTF•+ charge-separated state as the ultimate electron-transfer product. Due to distal separation of the positive and negative radical ions, long-lived charge-separated states persistent for about 0.35 μs was possible to accomplish, as shown by nanosecond transient absorption spectral studies.

Supramolecular complex of a fused zinc phthalocyanine-zinc porphyrin dyad assembled by two imidazole-C60 units: ultrafast photoevents.

A new zinc phthalocyanine-zinc porphyrin dyad (ZnPc-ZnP) fused through a pyrazine ring has been synthesized as a receptor for imidazole-substituted C60 (C60Im) electron acceptor. Self-assembly via metal-ligand axial coordination and the pertinent association constants in solution were determined by 1H-NMR, UV-Vis and fluorescence titration experiments at room temperature. The designed host was able to bind up to two C60Im electron acceptor guest molecules to yield C60Im:ZnPc-ZnP:ImC60 donor-acceptor supramolecular complex. The spectral data showed that the two binding sites behave independently with binding constants similar in magnitude. Steady-state fluorescence studies were indicative of an efficient singlet-singlet energy transfer from zinc porphyrin to zinc phthalocyanine within the fused dyad. Accordingly, the transient absorption studies covering a wide timescale of femto-to-milli seconds revealed ultrafast energy transfer from 1ZnP* to ZnPc (kEnT ∼ 1012 s-1) in the fused dyad. Further, a photo induced electron transfer was observed in the supramolecularly assembled C60Im:ZnPc-ZnP:ImC60 donor-acceptor complex leading to charge separated states, which persisted for about 200 ns.

A Strong Donor-Acceptor System Based on a Metal Chalcogenide Cluster and Porphyrin.

Although great progress has been made for charge transfer (CT) compounds of various organic donor-acceptor systems, no CT compounds containing both inorganic chalcogenide cluster anions and organic porphyrin cations have been reported. Herein, a germanium chalcogenide cluster (Ge4S104-) is chosen as an electron donor and a methylated tetrakis(4-pyridyl)porphyrin (5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin, TMPyP) is selected as an electron acceptor to create chalcogenide cluster-porphyrin CT compounds (TMPyP-Ge4S10)·5H2O (1) and (MnTMPyP-Ge4S10)·13H2O (2). Their crystal structures have been characterized by single-crystal X-ray diffraction. Compound 1 is an ionic CT salt assembled through interion interactions, and compound 2 is a neutral CT dyad formed by metal-ligand axial coordination of the chalcogenide cluster with manganese porphyrin. The strong charge transfer properties are revealed by electronic spectra, theoretical calculations, 1H NMR, and ESR. The CT intensity of the chalcogenide cluster-porphyrin system can be modulated by metalation. The fluorescence and photocurrent response properties of 1 and 2 are related to the CT intensity.

(Invited) Axially Assembled Photosynthetic Antenna-Reaction Center Mimics

A series of porphyrin based donor-acceptor conjugates in which the arrangement of various components are in perpendicular orientation to the porphyrin plane have been constructed and used to study the pathways of electron and energy transfer processes. The employed aluminum(III) porphyrin in these studies is found to be synthetically more advantageous as it provides reaction site on both faces of the porphyrin plane. The axial hydroxyl group on one side of the aluminum(III) porphyrin plane is able to form a covalent ester or ether bond with an energy harvester or electron acceptor while Lewis bases such as pyridine or an imidazole group form a metal-ligand axial coordination on other side of the plane hosting an electron donor or acceptor. The advantage of this configuration of the conjugates is that the donor and acceptor sides of the complex are located on opposite faces of the porphyrin which minimizes the rate of charge recombination. Moreover, the excited state \U0001d70b* orbital of porphyrin and axially coordinated ligand lie in the same space which causes an increase in the electronic coupling thus facilitating the electron/energy transfer processes. The distance dependence of sequential electron transfer in vertical, linear supramolecular triads constructed using tetrathiafulvalene (TTF), aluminum(III) porphyrin (AlPor) and fullerene (C60) entities will be discussed. Further, results of photoinduced energy transfer followed by electron transfer in antenna-reaction center mimicking BODIPY-AlPor-C60 supramolecular triads will be highlighted. Figure 1

A novel self-assembly with two acetohydrazide zinc porphyrins coordination polymer for supramolecular solar cells

Two new acetohydrazide zinc porphyrin with different donor units based Mn (Ⅱ) ion coordination polymers (CPsx, x=1,2) have been designed, synthesized, and well-characterized. Two coordination polymers and anchor porphyrin (ZnPA) self-assembly by metal-ligand axial coordination to modify the nano-structured TiO2 electrode surface has been investigated in photoelectrochemical device. Our results reveal that the self-assemblies devices show significantly improved photocurrent conversion efficiency. Particularly, CPs1 based solar cell showed higher short circuit current density and conversion efficiency. Their optical performance, electrochemical impedance spectroscopy and transient photovoltage decay were also investigated to further understand the photoelectrochemical results. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy (TEM), theory calculations and energy dispersive X-ray spectroscopy (EDX).

Geometry‐Controlled Photoinduced Charge Separation and Recombination in a Trans‐A2B2‐Functionalized Donor–Acceptor Conjugate Composed of a Multimodular Zinc Porphyrin and Fullerene

AbstractA novel trans‐A2B2‐functionalized multimodular zinc porphyrin (TPA‐BT)2ZnP has been synthesized through a multistep sitedirected synthesis as an electron donor for light‐energy‐harvesting applications. The Zn porphyrin was functionalized by appending two triphenylamine–bithiophene moieties (TPA‐BT) at the trans‐located meso‐positions of the porphyrin ring to improve the electron‐donor capability. Facile oxidation of the Zn porphyrin due to electron‐rich substituents was evidenced by cyclic voltammetry, and the spectrum of oxidized (TPA‐BT)2ZnP was obtained using spectroelectrochemical methods. The donor–acceptor conjugate was subsequently built by coordinating an electron acceptor, C60Im, through metal–ligand axial coordination. The conjugate was characterized by spectral, electrochemical, and computational techniques. The geometry and electronic structure of the (TPA‐BT)2ZnP:ImC60 conjugate, deduced from the B3LYP/6‐31G* method, revealed the frontier HOMO to be delocalized over the (TPA‐BT)2ZnP macrocycle whereas the LUMO was localized on the C60 entity. Free‐energy calculations performed according to Rehm–Weller's approach suggested the possibility of the occurrence of photoinduced electron transfer processes from the singlet excited Zn porphyrin to C60. Efficient photoinduced charge separation in the conjugate was demonstrated from studies involving femtosecond transient absorption techniques. The measured rate of charge separation was slightly higher than previously reported donor–acceptor systems formed from simple Zn porphyrin and C60Im due to facile oxidation of (TPA‐BT)2ZnP. The charge recombination rate was also found to be faster and this has been attributed to the closely located C60 and triphenylamine entities of (TPA‐BT)2ZnP, facilitating through‐space charge recombination process. The present study highlights the importance of the 3D organization of the self‐assembled donor–acceptor conjugate in governing the speed of electron transfer.

Two self-assemblies of Schiff base porphyrins to modify titanium dioxide electrodes for supramolecular solar cells

In this work, two Schiff base porphyrins have been successfully synthesized. The metal–ligand axial coordination assembling strategy has been used to organize two assemblies based on the two porphyrins appended isonicotinic acid ligands. Further, the assemblies were absorbed on the semiconducting TiO2 electrode surfaces by the carboxylic groups of isonicotinic acid ligands, and their photovoltaic performances were performed under irradiance of 100 mW cm−2 AM 1.5G sunlight. Photoelectrochemical studies show a significantly enhanced photovoltaic behavior for phenol-based zinc porphyrin assembly compared to pyridine-based zinc porphyrin assembly. The UV–Vis absorption, fluorescence spectra, molecular orbital patterns, and HOMO–LUMO energy gaps of the assemblies were also performed to further understand their photovoltaic features. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy.

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(n)Pcs) 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(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) 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(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-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(n)Pc 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.

High Potential Zinc Porphyrin-Fullerene Dyads: Formation and Electron Transfer Studies

Supramolecular dyads of photosensitizing halogenated zinc porphyrins (and halogenated zinc phthalocyanines) and redox active fulleropyrolidine derivatives with pyridine or imidazole ligands were constructed based on metal-ligand axial coordination approach. Spectroscopic characterization accompanied by steady-state absorption and fluorescence studies confirmed the high binding affinity of the high potential zinc porphyrin towards fullerene ligands that was also supported by computational studies. Qualitative Benesi-Hildebrand plots allowed us to calculate the association constant, K of the supramolecular dyads. The redox states of the donor and acceptor entities in the dyads were established from electrochemical investigations using cyclic and differential pulse voltammetry techniques. Free energy calculations using Weller’s approach suggested exergonic photoinduced electron transfer process for all of the studied systems. Pump-probe transient absorption studies at the femtosecond and nanosecond time scale confirmed the formation of cation and anion radical ions in the donor-acceptor supramolecular dyads. The kinetics of charge separation and charge recombination evaluated from the transient absorption studies revealed occurrence of ultrafast electron transfer events.

Electron Transfer Studies of High Potential Zinc Porphyrin–Fullerene Supramolecular Dyads

The ability of high oxidation potential zinc porphyrins acting as electron donors in photoinduced electron-transfer reactions is investigated. Donor–acceptor dyads were assembled via metal–ligand axial coordination of either pyridine or phenylimidazole functionalized fulleropyrrolidine with zinc porphyrin functionalized with different numbers of halogen substituents on the meso-aryl rings. Optical absorption studies on complex formation revealed relatively higher binding constants. Efficient quenching of fluorescence was observed for the newly assembled dyads, revealing their ability to undergo photoinduced events. Differential pulse voltammetry studies were performed to understand the structure–activity relationships with respect to the electron deficient nature of the porphyrins and to utilize these data to estimate free-energy change for charge-separation and charge-recombination processes. The absolute value of free-energy change for charge separation was found to be lower for halogenated porphyrins with higher oxidation potentials expecting to form high-energy radical ion pairs. Using femtosecond transient techniques, evidence for charge separation and kinetics of charge separation and recombination were obtained in toluene. The kinetic data obtained by analyzing the time profiles of the radical ions revealed occurrence of ultrafast charge separation and relatively slower charge recombination processes in the dyads. Notably, electron-transfer rates did not exactly follow the trends predicted based on Marcus theory of electron transfer. Donor–acceptor geometry and populating the triplet excited states of the sensitizers during charge recombination are considered to be possible reasons for this behavior.

Femtosecond Transient Absorption Study of Supramolecularly Assembled Metal Tetrapyrrole–TiO2 Thin Films

Photoexcited electron injection and back electron transfer dynamics of metal tetrapyrrole bound to TiO2 nanoparticle surfaces via the metal–ligand axial coordination approach have been investigated using femtosecond pump–probe transient spectroscopic technique. The employed metal tetrapyrroles include zinc and magnesium metalated meso-tetraarylporphyrins having halogen substituents on the peripheral aryl groups, perfluorinated zinc phthalocyanine derivatives, and zinc naphthalocyanine. The employed metal tetrapyrroles covered absorption at different portions of the visible and near-IR region of the spectrum with excited-state reduction potentials ranging between −0.61 eV and −1.34 V, that is, having energy higher than the TiO2 conduction band edge (−0.57 V vs NHE). Two linkers, pyridine and phenylimidazole, have been employed to visualize electronic coupling between the dye and metal oxide surface for optimal electron injection and back electron transfer dynamics. In agreement with the previously reported photocurrent generation of dye-sensitized solar cells constructed using this self-assembly approach (J. Am. Chem. Soc. 2009, 131, 14646), spectral evidence for electron injection from the excited metal tetrapyrrole to the TiO2 nanoparticle in the form of a tetrapyrrole radical cation has been obtained. The time profile of the π-cation radical of tetrapyrroles revealed the occurrence of ultrafast electron injection (time constant = 470–700 fs), while the back electron transfer processes were found to be complicated due to the intricate environment of the metallotetrapyrrole–TiO2 interface.

New self-assemblies with zinc meso-tetra[3-(1H-imidazol-1-yl)phenyl] porphyrin for use in supramolecular solar cells

In this work, a new zinc meso-tetra[3-(1H-imidazol-1-yl)phenyl]porphyrin (ZnP) was synthesized. Further, the porphyrin ZnP was immobilized by metal-ligand axial coordination (ZnP-A) and a metal-ligand edged binding approach (ZnP-Zn-A) on the nanostructured TiO2 electrode surface modified with coordinating ligand functionality, isonicotinic acid (A). The performances of the assemblies-sensitized solar cells were performed under irradiance of 100 mW cm−2 AM 1.5G sunlight. Photo-electrochemical studies reveal significantly improved performance of the assembly ZnP-A. These assemblies can afford a fertile base for further design and fabrication of new supramolecular solar cells in future.