The interlocking of ring and axle molecular components in rotaxanes provides a way to combine chromophoric, electron-donor and electron-acceptor moieties in the same molecular entity, in order to reproduce the features of photosynthetic reaction centers. To this aim, the photoinduced electron transfer processes involving a 1,8-naphthalimide chromophore, embedded in several rotaxane-based dyads, were investigated by steady-state and time-resolved absorption and luminescence spectroscopic experiments in the 300 fs-10 ns time window. Different rotaxanes built around the dialkylammonium/ dibenzo[24]crown-8 ether supramolecular motif were designed and synthesized to decipher the relevance of key structural factors, such as the chemical deactivation of the ammonium-crown ether recognition, the presence of a secondary site for the ring along the axle, and the covalent functionalization of the macrocycle with a phenothiazine electron donor. Indeed, the conformational freedom of these compounds gives rise to a rich dynamic behavior induced by light and may provide opportunities for investigating and understanding phenomena that take place in complex (bio)molecular architectures.

Phenomena involving electron transfer are ubiquitous in nature, photosynthesis and enzymes or protein activity being prominent examples. Their deep understanding thus represents a mandatory scientific goal. Moreover, controlling the separation of photogenerated charges is a crucial prerequisite in many applicative contexts, including quantum electronics, photo-electrochemical water splitting, photocatalytic dye degradation, and energy conversion. In particular, photoinduced charge separation is the pivotal step driving the storage of sun light into electrical or chemical energy. If properly mastered, these processes may also allow us to achieve a better command of information storage at the nanoscale, as required for the development of molecular electronics, optical switching, or quantum technologies, amongst others. In this Topical Review we survey recent progress in the understanding of ultrafast charge separation from photoexcited states. We report the state-of-the-art of the observation and theoretical description of charge separation phenomena in the ultrafast regime mainly focusing on molecular-and nano-sized solar energy conversion systems. In particular, we examine different proposed mechanisms driving ultrafast charge dynamics, with particular regard to the role of quantum coherence and electron-nuclear coupling, and link experimental observations to theoretical approaches based either on model Hamiltonians or on first principles simulations.

The insertion of a DNA nanolayer into polymer based solar cells, between the electron transport layer (ETL) and the active material, is proposed to improve the charge separation efficiency. Complete bulk heterojunction donor-acceptor solar cells of the layered type glass/electrode (indium tin oxide)/ETL/P3HT:PC70BM/hole transport layer/electrode (Ag) are investigated using femtosecond transient absorption spectroscopy both in the NIR and the UV-vis regions of the spectrum. The transient spectral changes indicate that when the DNA is deposited on the ZnO nanoparticles (ZnO-NPs) it can imprint a different long range order on the poly(3-hexylthiophene) (P3HT) polymer with respect to the non-ZnO-NPs/DNA containing cells. This leads to a larger delocalization of the initially formed exciton and its faster quenching which is attributed to more efficient exciton dissociation. Finally, the temporal response of the NIR absorption shows that the DNA promotes more efficient production of charge transfer states and free polarons in the P3HT cation indicating that the increased exciton dissociation correlates with increased charge separation.

A donor acceptor dyad composed of a BF2-chelated dipyrromethene (BODIPY) and a C-60 fullerene has been newly synthesized and characterized. The two moieties are linked by direct addition of an azido substituted BODIPY on the C-60, producing an imino fullerene BODIPY adduct. The photoinduced charge transfer process in this system was studied by ultrafast transient absorption spectroscopy. Electron transfer toward the fullerene was found to occur selectively exciting both the BODIPY chromophore at 475 nm and the C-60 unit at 266 nm on a time scale of a few picoseconds, but the dynamics of charge separation was different in the two cases. Eletrochemical studies provided information on the redox potentials of the involved species and spectroelectrochemical measurements allowed to unambiguously assign the absorption band of the oxidized BODIPY moiety, which helped in the interpretation of the transient absorption spectra. The experimental studies were complemented by a theoretical analysis based on DFT computations of the excited state energies of the two components and their electronic couplings, which allowed identification of the charge transfer mechanism and rationalization of the different kinetic behavior observed by changing the excitation conditions.

This article draws, with a simplified but rigorous approach, the typical procedure for the design and optimization of functional multicomponent structures for light to chemical energy conversion for two series of multipartite structures based on prototypical chromophores: polypyridyl metal complexes and porphyrinoids. Starting from a photophysical study performed by steady-state and time-resolved spectroscopic methods, the full deactivation dynamics of the light-absorbing chromophore(s) are disclosed. The preferred deactivation step (electron transfer in this case) is then optimized. This can be done by simply operating on the solvent, but also by changing structure/components that can alter electronic and nuclear factors, via continuous feedback with the research groups in charge of the synthesis. With a presentation suitable for a wide audience, it is here discussed how the effective design of functional multicomponent structures for charge separation can be achieved.

Excitation of the peripheral Zn porphyrin units in a noncovalent five-porphyrin array, formed by gable-like zinc(II) bisporphyrins and a central free-base meso-tetrakis(4-pyridyl)-porphyrin in a 2:1 ratio, (ZnP(2))(2).(TPyP), does not lead to a quantitative sensitization of the luminescence of the free-base porphyrin acceptor, even though there is an effective energy transfer. Time resolution of the luminescence evidences a quenching of TPyP upon sensitization by the peripheral ZnP(2). The time evolution of the TPyP fluorescence in the complex can be described by a bi-exponential fitting with a major component of 180 ps and a minor one of 5 ns, compared to an isolated TPyP lifetime of 9.4 ns. The two quenched lifetimes are shown to be correlated to the presence of 2:1 and 1:1 complexes, respectively. No quenching of TPyP fluorescence occurs in (ZnP(2))(2).(TPyP) at 77 K in a rigid solvent for which only an energy-transfer process (tau=150 +/- 10 ps) from peripheral ZnP(2) to the central TPyP is observed. An unusual HOMO-HOMO electron-transfer reaction from ZnP(2) to the excited TPyP units, responsible for the observed phenomena, is detected. The resulting charge-separated state, (ZnP(2))+(2).(TPyP)(-) is found to recombine to the ground state with a lifetime of 11 ns.

A series of perylene tetracarboxylic bisimides, substituted at the N-position with methoxyphenyl groups, have been synthesized together with model compounds and their photophysical properties have been investigated by means of steady-state and time-resolved spectroscopic techniques. The luminescence properties of the examined compounds vary remarkably with the substitution pattern, with emission quantum yields ranging from 1 to 10-2–10-3. The observed quenching of the luminescence is assigned to a photoinduced electron transfer (PET) from the electron-rich methoxybenzene unit to the perylene bisimide moiety. The radical anion of perylene bisimide has been detected by transient-absorption spectroscopy. The results could satisfactorily be explained by taking into consideration the redox potentials of the partners and the electron-releasing ability of each methoxy group in relation to its position with respect to N. Quantum-chemical calculations were also performed.

It is now quite well accepted that charge separation in PS2 reaction centers starts predominantly from the accessory chlorophyll B and not from the special pair P. To identify spectral signatures of B, and to further clarify the process of primary charge separation, we compared the femtosecond-infrared pump-probe spectra of the wild-type (WT) PS2 core complex from the cyanobacterium Synechocystis sp. PCC 6803 with those of two mutants in which the histidine residue axially coordinated to P (D2-His) has been changed to Ala or Gln. By analogy with the structure of purple bacterial reaction centers, the mutated histidine is proposed to be indirectly H-bonded to the C9=O carbonyl of the putative primary donor B through a water molecule. The constructed mutations are thus expected to perturb the vibrational properties of B by modifying the hydrogen bond strength, possibly by displacing the H-bonded water molecule, and to modify the electronic properties and the charge localization of the oxidized donor P: Analysis of steady-state light-induced Fourier transform infrared difference spectra of the WT and the D2-HisAla mutant indeed shows that a modification of the axially coordinating ligand to P induces a charge redistribution of P : In addition, a comparison of the time-resolved visible/midinfrared spectra of the WT and mutants has allowed us to investigate the changes in the kinetics of primary charge separation induced by the mutations and to propose a band assignment identifying the characteristic vibrations of B. © 2008 by the Biophysical Society.

The bichromophoric systems C2-PI, CXPI, and C3-PPI consisiting of corrole and perylene bisimide units and representing one of the rare cases of elaborate structures based on corrole, have been synthesized. Corroles C2 and C3 are, respectively, meso-substituted corroles with 2,6-dichlorophenyl and pentafluorophenyl substituents at the 5 and 15 positions. The three dyads were prepared by divergent strategy with the corrole-forming reaction as the last step of the sequence. C2-PI and C3-PI differ in the nature of the corroles, whereas C3-PI differs from C3-PPI in the presence of a further phenyl unit in the linker between photoactive units. The dyads display spectroscopic properties which are the superposition of the component spectra, indicating a very weak electronic coupling. Excitation of the corrole unit leads to charge separation with a rate which decreases from 2.4 x 10(10), to 5.0 x 10(9), and. to 4.9 x 10(7) s(-1) for C2-PI, C3-PI, and C3-PPI, respectively, where the reaction is characterized by a Delta G degrees > 0. Excitation of the perylene bisimide unit is followed by competing reactions of: 1) energy transfer to the corrole unit, which subsequently deactivates to the charge-separated state and; 2) electron transfer to directly form the charge-separated state. ne ratio of electron-to-energy-transfer rates is 9:1 and 1:1 for C3-PI and C3-PPI, respectively. The yield of charge separation is essentially 100% for C2-PI and C3-PI, and approximately 50% (excitation of peryleneimide) or 15% (excitation of the corrole) for C3-PPI. The lifetime of the charge-separated state, observed for the first time in corrole-based structures, is 540 ps for C2-PI, 2.5 ns for C3-PI, and 24 ns for C3-PPI, respectively. This is in agreement with an inverted behavior, according to Marcus theory.

A theoretical model of the quasistatic electric field, formed at the rear surface of a thin solid target irradiated by a ultraintense subpicosecond laser pulse, due to the appearance of a cloud of ultrarelativistic bound electrons, is developed. It allows one to correctly describe the spatial profile of the accelerating field and to predict the maximum energies and the energy spectra of the accelerated ions. The agreement of the theoretical expectations with the experimental data looks satisfactory in a wide range of conditions. Previsions of regimes achievable in the future are given.

Abstract: A triad D-Ir-A, where Ir is an IrIII bisterpyridine complex connected through an amidophenyl spacer to D, a triphenylamine electron donor, and to A, a naphthalene bisimide electron acceptor, has been synthesized and electrochemically investigated. The photoinduced processes in the triad, which is more than 4-nm long, have been characterized by steady-state and time-resolved optical spectroscopy by comparison with the model dyads D-Ir, Ir-A, and the reference monomers D, Ir, and A. A sequential electron transfer occurs upon excitation of the D and Ir units, leading to the charge-separated state D+-Ir-A in 100% yield and subsequently to D+-Ir-A in about 10% yield. The final charge-separated state has a lifetime at room temperature of 120 ms in air-free acetonitrile and of 100 ms in air-equilibrated solvent. Excitation of the A units does not yield intramolecular reactivity, but the resulting triplet-excited state localized on the acceptor, D-Ir-3A, displays intermolecular reactivity.