Probing the efficiency of electron transfer through porphyrin-based molecular wires

Electron transfer over long distances is important for many future applications in molecular electronics and solar energy harvesting. In these contexts, it is of great interest to find molecular systems that are able to efficiently mediate electrons in a controlled manner over nanometer distances, that is, structures that function as molecular wires. Here we investigate a series of butadiyne-linked porphyrin oligomers with ferrocene and fullerene (C60) terminals separated by one, two, or four porphyrin units (Pn, n = 1, 2, or 4). When the porphyrin oligomer bridges are photoexcited, long-range charge separated states are formed through a series of electron-transfer steps and the rates of photoinduced charge separation and charge recombination in these systems were elucidated using time-resolved absorption and emission measurements. The rates of long-range charge recombination, through these conjugated porphyrin oligomers, are remarkably fast (kCR2 = 15 - 1.3 x 108 s-1) and exhibit very weak distance dependence, particularly comparing the systems with n = 2 and n = 4. The observation that the porphyrin tetramer mediates fast long-range charge transfer, over 65 A, is significant for the application of these structures as molecular wires.     

Ultrafast spectral hole burning reveals the distinct chromophores in eumelanin and their common photoresponse

Eumelanin, the brown-black pigment found in organisms from bacteria to humans, dissipates solar energy and prevents photochemical damage. While the structure of eumelanin is unclear, it is thought to consist of an extremely heterogeneous collection of chromophores that absorb from the UV to the infrared, additively producing its remarkably broad absorption spectrum. However, the chromophores responsible for absorption by eumelanin and their excited state decay pathways remain highly uncertain. Using femtosecond broadband transient absorption spectroscopy, we address the excited state behavior of chromophore subsets that make up a synthetic eumelanin, DOPA melanin, and probe the heterogeneity of its chromophores. Tuning the excitation light over more than an octave from the UV to the visible and probing with the broadest spectral window used to study any form of melanin to date enable the detection of spectral holes with a linewidth of 0.6 eV that track the excitation wavelength. Transient spectral hole burning is a manifestation of extreme chemical heterogeneity, yet exciting these diverse chromophores unexpectedly produces a common photoinduced absorption spectrum and similar kinetics. This common photoresponse is assigned to the ultrafast formation of immobile charge transfer excitons that decay locally and that are formed among graphene-like chromophores in less than 200 fs. Raman spectroscopy reveals that chromophore heterogeneity in DOPA melanin arises from different sized domains of sp²-hybridized carbon and nitrogen atoms. Furthermore, we identify for the first time striking parallels between the excited state dynamics of eumelanin and disordered carbon nanomaterials, suggesting that they share common structural attributes.

Seeing the colors in black: ultrafast transient hole burning spectroscopy reveals the absorption properties of discrete chromophores and their interactions in the skin pigment eumelanin.     

Cooperative assembly of H-bonded rosettes inside a porphyrin nanoring

The melamine·barbiturate H-bonded rosette motif is of comparable dimensions and symmetry to the cavity of a butadiyne-linked 6-porphyrin nanoring. Functionalisation of each of the barbiturate components and the pyrimidine components of a H-bonded rosette with a pyridine ligand leads to a self-assembled hexapyridine ligand, which binds cooperatively to the zinc porphyrin nanoring. UV-vis-NIR and ¹H NMR experiments show that the 7-component assembly forms at concentrations at which neither the H-bonding interactions nor the zinc porphyrin–pyridine interactions are formed in the absence of one of the three components. The mean effective molarities of these rosette complexes are around 200 mM in chloroform at 298 K.

Mixing barbiturates and pyrimidines equipped with pyridine ligands to leads to self-assembly of a hexadentate rosette ligand, which is complementary to a hexameric zinc porphyrin macrocycle.     

Direct observation of o-benzyne formation in photochemical hexadehydro-Diels–Alder (hν-HDDA) reactions

Reactive ortho-benzyne derivatives are believed to be the initial products of liquid-phase [4 + 2]-cycloadditions between a 1,3-diyne and an alkyne via what is known as a hexadehydro-Diels–Alder (HDDA) reaction. The UV/VIS spectroscopic observation of o-benzyne derivatives and their photochemical dynamics in solution, however, have not been reported previously. Herein, we report direct UV/VIS spectroscopic evidence for the existence of an o-benzyne in solution, and establish the dynamics of its formation in a photoinduced reaction. For this purpose, we investigated a bis-diyne compound using femtosecond transient absorption spectroscopy in the ultraviolet/visible region. In the first step, we observe excited-state isomerization on a sub-10 ps time scale. For identification of the o-benzyne species formed within 50–70 ps, and the corresponding photochemical hexadehydro-Diels–Alder (hν-HDDA) reactions, we employed two intermolecular trapping strategies. In the first case, the o-benzyne was trapped by a second bis-diyne, i.e., self-trapping. The self-trapping products were then identified in the transient absorption experiments by comparing their spectral features to those of the isolated products. In the second case, we used perylene for trapping and reconstructed the spectrum of the trapping product by removing the contribution of irrelevant species from the experimentally observed spectra. Taken together, the UV/VIS spectroscopic data provide a consistent picture for o-benzyne derivatives in solution as the products of photo-initiated HDDA reactions, and we deduce the time scales for their formation.

We report the transient ultraviolet/visible absorption spectrum of an o-benzyne species in solution for the first time.     

Ortho C–H arylation of arenes at room temperature using visible light ruthenium C–H activation

A ruthenium-catalyzed ortho C–H arylation process is described using visible light. Using the readily available catalyst [RuCl₂(p-cymene)]₂, visible light irradiation was found to enable arylation of 2-aryl-pyridines at room temperature for a range of aryl bromides and iodides.

A ruthenium-catalyzed ortho C–H arylation process is described using visible light.     

A soft on/off switch based on the electrochemically reversible H–J interconversion of a floating porphyrin membrane

Soft molecular assemblies that respond reversibly to external stimuli are attractive materials as on/off switches, in optoelectronic, memory and sensor technologies. In this Edge Article, we present the reversible structural rearrangement of a soft porphyrin membrane under an electrical potential stimulus in the absence of solid-state architectures. The free-floating porphyrin membrane lies at the interface between immiscible aqueous and organic electrolyte solutions and is formed through interfacial self-assembly of zinc(ii) meso-tetrakis(4-carboxyphenyl)porphyrins (ZnPor). A potential difference between the two immiscible electrolyte solutions induces the intercalation of bis(triphenylphosphoranylidene)ammonium cations from the organic electrolyte that exchange with protons in the porphyrin membrane. In situ UV/vis absorbance spectroscopy shows that this ionic intercalation and exchange induces a structural interconversion of the individual porphyrin molecules in the membrane from an H- to a J-type molecular configuration. These structural rearrangements are reversible over 30 potential cycles. In situ polarisation-modulation fluorescence spectroscopy further provides clear evidence of structural interconversion of the porphyrin membrane, as intercalation of the organic electrolyte cations significantly affects the latter''s emissive properties. By adjusting the pH of the aqueous phase, additional control of the electrochemically reversible structural interconversion can be achieved, with total suppression at pH 3.

The structural rearrangement of a porphyrin membrane self-assembled at a “soft” liquid|liquid interface from a H- to J-molecular configuration is reversibly modulated by externally manipulating the interfacial Galvani potential difference.     

Iron porphyrin catalysed light driven C–H bond amination and alkene aziridination with organic azides

Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron–nitrene intermediate for subsequent C–N bond formation.

An iron(iii) porphyrin catalysed sp³ C–H amination and alkene aziridination with broad substrate scope under mild conditions is conducted, with selectivity through the use of organic azides as the nitrogen source under blue LED light irradiation.     

Control of electron transfer in a conjugated porphyrin dimer by selective excitation of planar and perpendicular conformers

A donor-acceptor system is presented in which the electron-transfer rates can be sensitively controlled by means of excitation wavelength and temperature. The electron donor is a butadiyne-linked zinc porphyrin dimer that is connected to a C(60) electron acceptor. The broad distribution of conformations allowed by the butadiyne linker makes it possible to selectively excite perpendicular or planar donor conformers and thereby prepare separate initial states with driving forces for electron transfer that differ by almost 0.2 eV. This, as well as significant differences in electronic coupling, leads to distinctly different rate constants for electron transfer, which in consequence can be controlled by changing excitation wavelength. By extending the system with a secondary donor (ferrocene), a second, long-range charge-separated state can be formed. This system has been used to test the influence of conformational heterogeneity on electron transfer mediated by the porphyrin dimer in the ground state. It was found that if the dimer is forced to a planar conformation by means of a bidentate ligand, the charge recombination rate increased by an order of magnitude relative to the unconstrained system. This illustrates how control of conformation of a molecular wire can affect its behaviour.     

Singlet fission in a hexacene dimer: energetics dictate dynamics

Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large.

We report the synthesis and photophysical characterization of highly exoergic singlet fission in a hexacene dimer revealing exciton dynamics that follow the energy gap law.     

Charge stabilization via electron exchange: excited charge separation in symmetric,central triphenylamine derived,dimethylaminophenyl–tetracyanobutadiene donor–acceptor conjugates

Photoinduced charge separation in donor–acceptor conjugates plays a pivotal role in technology breakthroughs, especially in the areas of efficient conversion of solar energy into electrical energy and fuels. Extending the lifetime of the charge separated species is a necessity for their practical utilization, and this is often achieved by following the mechanism of natural photosynthesis where the process of electron/hole migration occurs distantly separating the radical ion pairs. Here, we hypothesize and demonstrate a new mechanism to stabilize the charge separated states via the process of electron exchange among the different acceptor entities in multimodular donor–acceptor conjugates. For this, star-shaped, central triphenylamine derived, dimethylamine–tetracyanobutadiene conjugates have been newly designed and characterized. Electron exchange was witnessed upon electroreduction in conjugates having multiple numbers of electron acceptors. Using ultrafast spectroscopy, the occurrence of excited state charge separation, and the effect of electron exchange in prolonging the lifetime of charge separated states in the conjugates having multiple acceptors have been successfully demonstrated. This work constitutes the first example of stabilizing charge-separated states via the process of electron exchange.

The significance of electron exchange in stabilizing the charge-separated state is revealed in multi-modular donor–acceptor conjugates.     

Aggregation-free and high stability core–shell polymer nanoparticles with high fullerene loading capacity,variable fullerene type,and compatibility towards biological conditions

Fullerenes have unique structural and electronic properties that make them attractive candidates for diagnostic, therapeutic, and theranostic applications. However, their poor water solubility remains a limiting factor in realizing their full biomedical potential. Here, we present an approach based on a combination of supramolecular and covalent chemistry to access well-defined fullerene-containing polymer nanoparticles with a core–shell structure. In this approach, solvophobic forces and aromatic interactions first come into play to afford a micellar structure with a poly(ethylene glycol) shell and a corannulene-based fullerene-rich core. Covalent stabilization of the supramolecular assembly then affords core-crosslinked polymer nanoparticles. The shell makes these nanoparticles biocompatible and allows them to be dried to a solid and redispersed in water without inducing interparticle aggregation. The core allows a high content of different fullerene types to be encapsulated. Finally, covalent stabilization endows nanostructures with stability against changing environmental conditions.

A polymer nanoparticle approach to biorelevant and robust fullerene nanoparticles is presented.     

Anion-enhanced excited state charge separation in a spiro-locked N-heterocycle-fused push-pull zinc porphyrin

A new type of push–pull charge transfer complex, viz., a spiro-locked N-heterocycle-fused zinc porphyrin, ZnP-SQ, is shown to undergo excited state charge separation, which is enhanced by axial F⁻ binding to the Zn center. In this push–pull design, the spiro-quinone group acts as a ‘lock’ promoting charge transfer interactions by constraining mutual coplanarity of the meso-phenol-substituted electron-rich Zn(ii) porphyrin and an electron deficient N-heterocycle, as revealed by electrochemical and computational studies. Spectroelectrochemical studies have been used to identify the spectra of charge separated states, and charge separation upon photoexcitation of ZnP has been unequivocally established by using transient absorption spectroscopic techniques covering wide spatial and temporal regions. Further, global target analysis of the transient data using GloTarAn software is used to obtain the lifetimes of different photochemical events and reveal that fluoride anion complexation stabilizes the charge separated state to an appreciable extent.

A new type of push–pull charge transfer complex, viz., a spiro-locked N-heterocycle-fused zinc porphyrin, ZnP-SQ, is shown to undergo excited state charge separation, which is enhanced by axial F⁻ binding to the Zn center.     

Cation recognition on a fullerene-based macrocycle

Heterocyclic orifices in cage-opened fullerene derivatives are regarded as potential ligands toward metals or ions, being reminiscent of truncated fullerenes as a hypothetical class of macrocycles with spherical π-conjugation. Among a number of cage-opened examples reported thus far, the coordination ability and dynamic behavior in solution still remained unclear due to difficulties in structural determination with multiple coordination sites on the macrocycles. Herein, we present the detailed solution dynamics of a cage-opened C₆₀ derivative bearing a diketo bis(hemiketal) moiety in the presence of alkali metal ions. The NMR spectroscopy disclosed the coordination behavior which is identified as a two-step process with a 1 : 2 stoichiometry. Upon coordination to the Li⁺ ion, the macrocycle largely varies its properties, i.e., increased absorption coefficients in the visible region due to weakly-allowed charge transfer transitions as well as the inner potential field from neutral to positive by the charge delocalization along with the spherical π-surface. The Li⁺-complexes formed in situ underwent unprecedented selective dehydroxyhydrogenation under high-pressure conditions. These findings would facilitate further studies on fullerene-based macrocycles as metal sensors, bulky ligands in organic reactions, and ion carriers in batteries and biosystems.

A fullerene-based Lewis-basic macrocyclic ligand underwent complexation with alkali-metal ions in 1 : 1 and 1 : 2 fashions, resulting in considerable perturbation to absorption properties as well as the potential surface inside the cage.     

The central role of the metal ion for photoactivity: Zn– vs. Ni–Mabiq

Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts remains a challenge. We here present the photochemical and photophysical properties of a Ni–Mabiq catalyst ([Ni^II(Mabiq)]OTf (1); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N₆)—and of a Zn-containing analogue ([Zn^II(Mabiq)OTf] (2))—using steady state and time resolved optical spectroscopy, time-dependent density functional theory (TDDFT) calculations, and reactivity studies. The Ni and Zn complexes exhibit similar absorption spectra, but markedly different photochemical properties. These differences arise because the excited states of 2 are ligand-localized, whereas metal-centered states account for the photoactivity of 1. The distinct properties of the Ni and Zn complexes are manifest in their behavior in the photo-driven aza-Henry reaction and oxidative coupling of methoxybenzylamine.

The development of earth-abundant photoredox catalysts remains a challenge. Studies of Ni- and Zn-Mabiq complexes demonstrate how the coordinating metal ion influences the photochemistry, photodynamics and reactivity of photocatalysts.     

Conformation effect of oligosilane linker on photoinduced electron transfer of tetrasilane-linked zinc porphyrin–[60]fullerene dyads

A series of zinc porphyrin–[60]fullerene dyads linked by conformation-constrained tetrasilanes and permethylated tetrasilane have been synthesized for the evaluation of the conformation effect of the tetrasilane linkers on the photoinduced electron transfer. The excited-state dynamics of these dyads have been studied using the time-resolved fluorescence and absorption measurements. The fluorescence of the zinc porphyrin moiety in each dyad was quenched by the electron transfer to the fullerene moiety. The transient absorption measurements revealed that the final state of the excited-state process was a radical ion pair with a radical cation on the zinc porphyrin moiety and a radical anion on the fullerene moiety as a result of the charge separation. The charge separation and charge recombination rates were found to show only slight conformation dependence of the tetrasilane linkers, which is characteristic for the Si-linkages.     

Effects of ligands on the migratory insertion of alkenes into rhodium–oxygen bonds

Migratory insertions of olefins into metal–oxygen bonds are elementary steps of important catalytic processes, but well characterised complexes that undergo this reaction are rare, and little information on the effects of ancillary ligands on such reactions has been gained. We report a series of alkoxo alkene complexes of rhodium(i) that contain a range of bidentate ligands and that undergo insertion of the alkene. Our results show that complexes containing less electron-donating ancillary ligands react faster than their counterparts containing more electron-donating ancillary ligands, and that complexes possessing ligands with larger bite angles react faster than those with smaller bite angles. External added ligands had several effects on the reactions, including an inhibition of olefin isomerisation in the product and acceleration of the displacement of the product from complexes of ancillary ligands with small bite angles. Complementary computational studies help elucidate the details of these insertion processes.

A series of diphosphine-ligated rhodium(i) alkoxo alkene complexes is reported and the migratory insertion of the alkene moiety into the rhodium–oxygen bond in these complexes was studied, revealing the effects of the ligand on the insertion process.     

Two-photon absorption properties of self-assemblies of butadiyne-linked bis(imidazolylporphyrin)

Supramolecular porphyrin self-assemblies have been prepared from butadiyne-linked bis(imidazolylporphyrin) by complementary coordination of imidazole to zinc, and their two-photon absorption (2PA) and higher-order nonlinear absorption properties were investigated over femtosecond time scales using an open-aperture Z-scan method. The self-assembled porphyrin dimer of the conjugated monozinc bisporphyrin 7D was shown to have a large 2PA cross section (7.6 x 10(3) GM, where 1 GM = 10(-50) cm(4) s molecule(-1) photon(-1)) at 887 nm. By comparison of this result with that for a meso-meso-linked porphyrin array without the butadiyne connection (3.7 x 10(2) GM at 964 nm), it was demonstrated that the predominant factor in this significant enhancement of the cross section was the expansion of porphyrin-porphyrin pi-conjugation. Self-coordination and monozinc metalation were also found to be contributing factors. Furthermore, a novel self-assembled porphyrin polymer 8P consisting of a biszinc complex with a mean molecular weight of M(n) = 1.5 x 10(5) Da was shown to exhibit an extraordinarily large two-photon absorption cross section (4.4 x 10(5) GM at 873 nm). Nanosecond Z-scan experiments for 7D and 8P were also undertaken and resulted in the measurement of large effective 2PA cross sections, including the excited-state absorption (2.1 x 10(5) GM for 7D and 2.2 x 10(7) GM for 8P, respectively). Finally, three-photon absorption was observed by femtosecond Z-scan experiments at 1188 nm (7.1 x 10(-89) m(6) s(2)) and 1282 nm (1.8 x 10(-89) m(6) s(2)), an observation which is the first of its kind in porphyrin chemistry.     

Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides

Ruthenium polypyridyl complexes which can sensitise the photo-oxidation of nucleic acids and other biological molecules show potential for photo-therapeutic applications. In this article a combination of transient visible absorption (TrA) and time-resolved infra-red (TRIR) spectroscopy are used to compare the photo-oxidation of guanine by the enantiomers of [Ru(TAP)₂(dppz)]²⁺ in both polymeric {poly(dG-dC), poly(dA-dT) and natural DNA} and small mixed-sequence duplex-forming oligodeoxynucleotides. The products of electron transfer are readily monitored by the appearance of a characteristic TRIR band centred at ca. 1700 cm⁻¹ for the guanine radical cation and a band centered at ca. 515 nm in the TrA for the reduced ruthenium complex. It is found that efficient electron transfer requires that the complex be intercalated at a G-C base-pair containing site. Significantly, changes in the nucleobase vibrations of the TRIR spectra induced by the bound excited state before electron transfer takes place are used to identify preferred intercalation sites in mixed-sequence oligodeoxynucleotides and natural DNA. Interestingly, with natural DNA, while it is found that quenching is inefficient in the picosecond range, a slower electron transfer process occurs, which is not found with the mixed-sequence duplex-forming oligodeoxynucleotides studied.

Efficient electron transfer requires the complex to be intercalated at a G-C base-pair. Identification of preferred intercalation sites is achieved by TRIR monitoring of the nucleobase vibrations before electron transfer.     

Phenylene-bridged bis(benzimidazolium) (BBIm2+): a dicationic organic photoredox catalyst

A dicationic photoredox catalyst composed of phenylene-bridged bis(benzimidazolium) (BBIm²⁺) was designed, synthesised and demonstrated to promote the photochemical decarboxylative hydroxylation and dimerisation of carboxylic acids. The catalytic activity of BBIm²⁺ was higher than that for a monocation analogue, suggesting that the dicationic nature of BBIm²⁺ plays a key role in these decarboxylative reactions. The rate constant for the decay of the triplet–triplet absorption of the excited BBIm²⁺ increased with increasing concentration of the carboxylate anion with a saturated dependence, suggesting that photoinduced electron transfer occurs within the ion pair complex composed of the triplet excited state of BBIm²⁺ and a carboxylate anion.

A new organic dication, phenylene-bridged bis(benzimidazolium), catalyses the photochemical decarboxylative hydroxylation and dimerisation of carboxylic acids.     

Aperiodic metal–organic frameworks

Metal–organic frameworks (MOFs) represent one of the most diverse structural classes among solid state materials, yet few of them exhibit aperiodicity, or the existence of long-range order in the absence of translational symmetry. From this apparent conflict, a paradox has emerged: even though aperiodicity frequently arises in materials that contain the same bonding motifs as MOFs, aperiodic structures and MOFs appear to be nearly disjoint classes. In this perspective, we highlight a subset of the known aperiodic coordination polymers, including both incommensurate and quasicrystalline structures. We further comment upon possible reasons for the absence of such structures and propose routes to potentially access aperiodic MOFs.

This perspective discusses progress and future directions in metal–organic frameworks with aperiodic structures. Reported quasicrystalline and incommensurate materials are presented, and pathways towards designing new such materials are provided.