Borylation in the Second Coordination Sphere of Fe(II) Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics

Second coordination sphere interactions of cyanido complexes with hydrogen-bonding solvents and Lewis acids are known to influence their electronic structures, whereby the non-labile attachment of B(C6F5)3 resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two FeII cyanido complexes in a systematic manner by comparing five different compounds and using a range of experimental techniques. Electrochemical measurements indicate that borylation entails a stabilization of the FeII-based t2g-like orbitals by up to 1.65 eV, and this finding was confirmed by Mössbauer spectroscopy. This change in the electronic structure has a profound impact on the UV–vis absorption properties of the borylated complexes compared to the non-borylated ones, shifting their metal-to-ligand charge transfer (MLCT) absorption bands over a wide range. Ultrafast UV–vis transient absorption spectroscopy provides insight into how borylation affects the excited-state dynamics. The lowest metal-centered (MC) excited states become shorter-lived in the borylated complexes compared to their cyanido analogues by a factor of ∼10, possibly due to changes in outer-sphere reorganization energies associated with their decay to the electronic ground state as a result of B(C6F5)3 attachment at the cyanido N lone pair

The nature of singlet exciton fission in carotenoid aggregates.

Singlet exciton fission allows the fast and efficient generation of two spin triplet states from one photoexcited singlet. It has the potential to improve organic photovoltaics, enabling efficient coupling to the blue to ultraviolet region of the solar spectrum to capture the energy generally lost as waste heat. However, many questions remain about the underlying fission mechanism. The relation between intermolecular geometry and singlet fission rate and yield is poorly understood and remains one of the most significant barriers to the design of new singlet fission sensitizers. Here we explore the structure-property relationship and examine the mechanism of singlet fission in aggregates of astaxanthin, a small polyene. We isolate five distinct supramolecular structures of astaxanthin generated through self-assembly in solution. Each is capable of undergoing intermolecular singlet fission, with rates of triplet generation and annihilation that can be correlated with intermolecular coupling strength. In contrast with the conventional model of singlet fission in linear molecules, we demonstrate that no intermediate states are involved in the triplet formation: instead, singlet fission occurs directly from the initial 1B(u) photoexcited state on ultrafast time scales. This result demands a re-evaluation of current theories of polyene photophysics and highlights the robustness of carotenoid singlet fission.This work was supported by the EPSRC (UK) (EP/G060738/ 1), the European Community (LASERLAB-EUROPE, grant agreement no. 284464, EC’s Seventh Framework Programme; and Marie-Curie ITN-SUPERIOR, PITN-GA-2009-238177), and the Winton Programme for the Physics of Sustainability. G.C. acknowledges support by the European Research Council Advanced Grant STRATUS (ERC-2011-AdG No. 291198). J.C. acknowledges support by the Royal Society Dorothy Hodgkin Fellowship and The University of Sheffield’s Vice- Chancellor’s Fellowship scheme.This is the final published version. It was first made available by ACS at http://pubs.acs.org/doi/abs/10.1021/jacs.5b01130

Ultrafast Electron Dynamics in Solar Energy Conversion

Electrons are the workhorses of solar energy conversion. Conversion of the energy of light to electricity in photovoltaics, or to energy-rich molecules (solar fuel) through photocatalytic processes, invariably starts with photoinduced generation of energy-rich electrons. The harvesting of these electrons in practical devices rests on a series of electron transfer processes whose dynamics and efficiencies determine the function of materials and devices. To capture the energy of a photogenerated electron-hole pair in a solar cell material, charges of opposite sign have to be separated against electrostatic attractions, prevented from recombining and being transported through the active material to electrodes where they can be extracted. In photocatalytic solar fuel production, these electron processes are coupled to chemical reactions leading to storage of the energy of light in chemical bonds. With the focus on the ultrafast time scale, we here discuss the light-induced electron processes underlying the function of several molecular and hybrid materials currently under development for solar energy applications in dye or quantum dot-sensitized solar cells, polymer-fullerene polymer solar cells, organometal halide perovskite solar cells, and finally some photocatalytic systems

Time-Resolved Laser Spectroscopy in Molecular Devices for Solar Energy Conversion

A complete characterization of solar energy conversion devices and the processes underlying their function is a challenge, and require a multitude of different experimental methods. This chapter discusses investigations of molecular solar cells and solar fuels devices by time-resolved laser spectroscopic methods. These methods have established important concepts we now use for understanding the function of devices for solar energy conversion into primary products. We give examples of scientific insight provided by ultrafast methods using detection in the regions from X-ray to THz radiation, and particularly highlight the case where the use of different methods has provided complementary information. Charge collection and solar fuel catalysis on the other hand occur on longer time scales, which opens for the use of time-resolved magnetic resonance and microwave conductivity methods. We also point out that, with suitable precautions, time-resolved laser spectroscopy is able to give information relevant for in operando device condition

Band-selective dynamics in charge-transfer excited iron carbene complexes

Ultrafast dynamics of photoinduced charge transfer processes in light-harvesting systems based on Earth-abundant transition metal complexes are of current interest for the development of molecular devices for solar energy conversion applications. A combination of ultrafast spectroscopy and first principles quantum chemical calculations of a recently synthesized iron carbene complex is used to elucidate the ultrafast excited state evolution processes in these systems with particular emphasis on investigating the underlying reasons why these complexes show promise in terms of significantly extended lifetimes of charge transfer excited states. Together, our results challenge the traditional excited state landscape for iron-based light harvesting transition metal complexes through radically different ground and excited state properties in alternative oxidation states. This includes intriguing indications of rich band-selective excited state dynamics on ultrafast timescales that are interpreted in terms of excitation energy dependence for excitations into a manifold of charge-transfer states. Some implications of the observed excited state properties and photoinduced dynamics for the utilization of iron carbene complexes for solar energy conversion applications are finally discussed

FeII Hexa N-Heterocyclic Carbene Complex with a 528 ps Metal-To-Ligand Charge-Transfer Excited-State Lifetime

The iron carbene complex [FeII(btz)3](PF6)2 (where btz = 3,3′-dimethyl-1,1′-bis(p-Tolyl)-4,4′-bis(1,2,3-Triazol-5-ylidene)) has been synthesized, isolated, and characterized as a low-spin ferrous complex. It exhibits strong metal-To-ligand charge transfer (MLCT) absorption bands throughout the visible spectrum, and excitation of these bands gives rise to a 3MLCT state with a 528 ps excited-state lifetime in CH3CN solution that is more than one order of magnitude longer compared with the MLCT lifetime of any previously reported FeII complex. The low potential of the [Fe(btz)3]3+/[Fe(btz)3]2+ redox couple makes the 3MLCT state of [FeII(btz)3]2+ a potent photoreductant that can be generated by light absorption throughout the visible spectrum. Taken together with our recent results on the [FeIII(btz)3]3+ form of this complex, these results show that the FeII and FeIII oxidation states of the same Fe(btz)3 complex feature long-lived MLCT and LMCT states, respectively, demonstrating the versatility of iron N-heterocyclic carbene complexes as promising light-harvesters for a broad range of oxidizing and reducing conditions

Dye-sensitized solar cells based on Fe N-heterocyclic carbene photosensitizers with improved rod-like push-pull functionality

A new generation of octahedral iron(ii)-N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push-pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push-pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I−/I3−redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO2. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO2. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO2back to the oxidized dye, leaving only 5-10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6-8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work