A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence.

Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

Publisher's Note: Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [Co(terpy)_{2}]

This corrects the article DOI: 10.1103/PhysRevLett.117.013002.

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy.

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeII NHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3 MLCT state, from the initially excited 1 MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3 MC state, in competition with vibrational relaxation and cooling to the relaxed 3 MLCT state. The relaxed 3 MLCT state then decays much more slowly (7.6 ps) to the 3 MC state. The 3 MC state is rapidly (2.2 ps) deactivated to the ground state. The 5 MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3 MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

Synthesis of Organic Super-Electron-Donors by Reaction of Nitrous Oxide with N-Heterocyclic Olefins.

The reaction of nitrous oxide (N2O) with N-heterocyclic olefins (NHOs) results in cleavage of the N-O bond and formation of azo-bridged NHO dimers. The latter represent very electron-rich compounds with a low ionization energy. Cyclic voltammetry studies show that the dimers can be classified as new organic super-electron-donors, with a reducing power similar to what is found for tetraazafulvalene derivatives. Mild oxidants are able to convert the neutral dimers into radical cations, which can be isolated. Further oxidation gives stable dications.

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.

Lewis Acid-Mediated One-Electron Reduction of Nitrous Oxide.

The one-electron reduction of nitrous oxide (N2 O) was achieved using strong Lewis acids E(C6 F5 )3 (E=B or Al) in combination with metallocenes. In the case of B(C6 F5 )3 , electron transfer to N2 O required a powerful reducing agent such as Cp*2 Co (Cp*=pentamethylcyclopentadienyl). In the presence of Al(C6 F5 )3 , on the other hand, the reactions could be performed with weaker reducing agents such as Cp*2 Fe or Cp2 Fe (Cp=cyclopentadienyl). The Lewis acid-mediated electron transfer from the metallocene to N2 O resulted in cleavage of the N-O bond, generating N2 and the oxyl radical anion [OE(C6 F5 )3 ]⋅- . The latter is highly reactive and engages in C-H activation reactions. It was possible to trap the radical by addition of the Gomberg dimer, which acts as a source of the trityl radical.

Trimethylsilyl-Induced N-O Bond Cleavage in Nitrous Oxide-Derived Aminodiazotates.

The chemical activation of nitrous oxide (N2O) typically results in O-atom transfer and the extrusion of N2 gas. In contrast, reactions of N-trimethylsilyl (TMS)-substituted amides with N2O give inorganic or organic azides, with concomitant formation of silanols or siloxanes. N-TMS-substituted amides are also able to induce N-O bond cleavage in N2O-derived dialkylaminodiazotates, generating tetrazene salts. These results indicate the potential of silyl groups in devising transformations, in which N2O acts as an N-atom donor.

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN)4]2.

The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN)4]2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile.1,2 In the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet (3MC) character, unlike other reported six-coordinate Fe(ii)-centered coordination compounds, which form MC quintet (5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN)4]2- allows us to infer the influence of the solvent on the electronic structure of the complex. Furthermore, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.

Intercomparison on Four Irrigated Cropland Maps in Mainland China.

Wide-coverage spatial information on irrigated croplands is a vital foundation for food security and water resources studies at the regional level. Several global irrigated-cropland maps have been released to the public over the past decade due to the efforts of the remote sensing community. However, the consistency and discrepancy between these maps is largely unknown because of a lack of comparative studies, limiting their use and improvement. To close this knowledge gap, we compared the latest four irrigated-cropland datasets (GMIA, GRIPC, GlobCover, and GFSAD) in mainland China. First, the four maps were compared quantitatively and neutral regional- and provincial-level statistics of the relative proportions of irrigated land were obtained through regression analysis. Second, we compared the similarities and discrepancies of the datasets on spatial grids. Furthermore, the contributions of mosaic cropland pixels in GlobCover and GFSAD were also analyzed because of their extensive distribution and ambiguous content. Results showed that GMIA has the lowest dispersion and best statistical correlation followed by GRIPC, while the corresponding features of GlobCover and GFSAD are approximately equal. Spatial agreement of the four maps is higher in eastern than western China, and disagreement is contributed mostly by GlobCover and GFSAD. However, divergence exists in the ratios of the different agreement levels, as well as their sources, on a regional scale. Mosaic pixels provide more than half of the irrigated areas for GlobCover and GFSAD, and they include both correct and incorrect information. Our results indicate a need for a uniform quantitative classification system and for greater focus on heterogeneous regions. Furthermore, the results demonstrate the advantage of numerical restriction in the calculations. Therefore, special attention should be paid to integrating databases and to exploring remote sensing features and methods for spatial reconstruction and identification of untypical irrigation areas.

Fe N-Heterocyclic Carbene Complexes as Promising Photosensitizers.

The photophysics and photochemistry of transition metal complexes (TMCs) has long been a hot field of interdisciplinary research. Rich metal-based redox processes, together with a high variety in electronic configurations and excited-state dynamics, have rendered TMCs excellent candidates for interconversion between light, chemical, and electrical energies in intramolecular, supramolecular, and interfacial arrangements. In specific applications such as photocatalytic organic synthesis, photoelectrochemical cells, and light-driven supramolecular motors, light absorption by a TMC-based photosensitizer and subsequent excited-state energy or electron transfer constitute essential steps. In this context, TMCs based on rare and expensive metals, such as ruthenium and iridium, are frequently employed as photosensitizers, which is obviously not ideal for large-scale implementation. In the search for abundant and environmentally benign solutions, six-coordinate Fe(II) complexes (Fe(II)L6) have been widely considered as highly desirable alternatives. However, not much success has been achieved due to the extremely short-lived triplet metal-to-ligand charge transfer ((3)MLCT) excited state that is deactivated by low-lying metal-centered (MC) states on a 100 fs time scale. A fundamental strategy to design useful Fe-based photosensitizers is thus to destabilize the MC states relative to the (3)MLCT state by increasing the ligand field strength, with special focus on making eg σ* orbitals on the Fe center energetically less accessible. Previous efforts to directly transplant successful strategies from Ru(II)L6 complexes unfortunately met with limited success in this regard, despite their close chemical kinship. In this Account, we summarize recent promising results from our and other groups in utilizing strongly σ-donating N-heterocyclic carbene (NHC) ligands to make strong-field Fe(II)L6 complexes with significantly extended (3)MLCT lifetimes. Already some of the first homoleptic bis(tridentate) complexes incorporating (CNHC^Npyridine^CNHC)-type ligands gratifyingly resulted in extension of the (3)MLCT lifetime by more than 2 orders of magnitude compared to the parental [Fe(tpy)2](2+) (tpy = 2,2':6',2″-terpyridine) complex. Quantum chemical (QC) studies also revealed that the (3)MC instead of the (5)MC state likely dictates the deactivation of the (3)MLCT state, a behavior distinct from traditional Fe(II)L6 complexes but rather resembling Ru analogues. A heteroleptic Fe(II) NHC complex featuring mesoionic bis(1,2,3-triazol-5-ylidene) (btz) ligands also delivered a 100-fold elongation of the (3)MLCT lifetime relative to its parental [Fe(bpy)3](2+) (bpy = 2,2'-bipyridine) complex. Again, a Ru-like deactivation mechanism of the (3)MLCT state was indicated by QC studies. With a COOH-functionalized homoleptic complex, a record (3)MLCT lifetime of 37 ps was recently observed on an Al2O3 nanofilm. As a proof of concept, it was further demonstrated that the significant improvement in the (3)MLCT lifetime indeed benefits efficient light harvesting with Fe(II) NHC complexes. For the first time, close-to-unity electron injection from the lowest-energy (3)MLCT state to a TiO2 nanofilm was achieved by a stable Fe(II) complex. This is in complete contrast to conventional Fe(II)L6-derived photosensitizers that could only make use of high-energy photons. These exciting results significantly broaden the understanding of the fundamental photophysics and photochemistry of d(6) Fe(II) complexes. They also open up new possibilities to develop solar energy-converting materials based on this abundant, inexpensive, and intrinsically nontoxic element.

Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [Co(terpy)_{2}]

We study the structural dynamics of photoexcited [Co(terpy)_{2}]^{2+} in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ∼7 ps.

A heteroleptic ferrous complex with mesoionic bis(1,2,3-triazol-5-ylidene) ligands: taming the MLCT excited state of iron(II).

Strongly σ-donating N-heterocyclic carbenes (NHCs) have revived research interest in the catalytic chemistry of iron, and are now also starting to bring the photochemistry and photophysics of this abundant element into a new era. In this work, a heteroleptic Fe(II) complex (1) was synthesized based on sequentially furnishing the Fe(II) center with the benchmark 2,2'-bipyridine (bpy) ligand and the more strongly σ-donating mesoionic ligand, 4,4'-bis(1,2,3-triazol-5-ylidene) (btz). Complex 1 was comprehensively characterized by electrochemistry, static and ultrafast spectroscopy, and quantum chemical calculations and compared to [Fe(bpy)3](PF6)2 and (TBA)2[Fe(bpy)(CN)4]. Heteroleptic complex 1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic Fe(II) NHC complex. The combination of the mesoionic nature of btz and the heteroleptic structure effectively destabilizes the metal-centered (MC) states relative to the triplet metal-to-ligand charge transfer ((3)MLCT) state in 1, rendering it a lifetime of 13 ps, the longest to date of a photochemically stable Fe(II) complex. Deactivation of the (3)MLCT state is proposed to proceed via the (3)MC state that strongly couples with the singlet ground state.

Highly accurate excited-state structure of [Os(bpy)2dcbpy](2+) determined by X-ray transient absorption spectroscopy.

Determining the electronic and geometric structures of photoexcited transient species with high accuracy is crucial for understanding their fundamental photochemistry and controlling their photoreactivity. We have applied X-ray transient absorption spectroscopy to measure the XANES and EXAFS spectra of a dilute (submillimolar) solution of the osmium(II) polypyridyl complex [Os(bpy)2dcbpy](PF6)2 (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) (OsL2L') in methanol at the Os LIII edge. We have obtained spectra of superb quality for both the ground state and the photoinduced (3)MLCT excited state that have allowed us not only to extract detailed information about the Os 5d orbitals but also to resolve very small differences of 0.010 ± 0.008 Å in the average Os-N bond lengths of the ground and excited states. Theoretical calculations using a recently developed DFT-based approach support the measured electronic structures and further identify the nature of the molecular orbitals that contribute to the main absorption bands in the XANES spectra.

Photoacoustic Imaging-Guided Self-Adaptive Hyperthermia Supramolecular Cascade Nano-Reactor for Diabetic Periodontal Bone Regeneration.

Commencing with the breakdown of the diabetic osteoimmune microenvironment, multiple pathogenic factors, including hyperglycemia, inflammation, hypoxia, and deleterious cytokines, are conjointly involved in the progression of diabetic periodontal bone regeneration. Based on the challenge of periodontal bone regeneration treatment and the absence of real-time feedback of blood oxygen fluctuation in diabetes mellitus, a novel self-adaptive hyperthermia supramolecular cascade nano-reactor ACFDG is constructed via one-step supramolecular self-assembly strategy to address multiple factors in diabetic periodontal bone regeneration. Hyperthermia supramolecular ACFDG possesses high photothermal conversion efficiency (32.1%), and it can effectively inhibit the vicious cycle of ROS-inflammatory cascade through catalytic cascade reactions, up-regulate the expression of heat shock proteins (HSPs) under near-infrared (NIR) irradiation, which promotes periodontal bone regeneration. Remarkably, ACFDG can provide real-time non-invasive diagnosis of blood oxygen changes during periodontal bone regeneration through photoacoustic (PA) imaging, thus can timely monitor periodontal hypoxia status. In conclusion, this multifunctional supramolecular nano-reactor combined with PA imaging for real-time efficacy monitoring provides important insights into the biological mechanisms of diabetic periodontal bone regeneration and potential clinical theranostics.

Large pore size and high porosity of TiO2 photoanode for excellent photovoltaic performance of CdS quantum dot sensitized solar cell.

While holding great potential as sunlight absorbers, quantum dots (QDs), which are generally much larger than dye molecule in size, which makes it more difficult to deposit them on the surface of TiO2. As a result, relatively low QD loading is now one of the most challenging issues for improving the photovoltaic performance of QD-sensitized solar cells (QDSSC). In this study, TiO2 photoanodes with different pore sizes and porosities were constructed by systematically varying the solid content of the TiO2 paste. It was confirmed that reducing the solid content resulted in both larger pore sizes and higher porosities. CdS quantum dots were then deposited on these different electrodes by the successive ionic layer adsorption and reaction (SILAR) method, with either 4 or 7 repetitive cycles. By correlating the photovoltaic performances of QDSSCs with different solid contents of TiO2 paste and number of SILAR cycles of CdS QD deposition, it was found that the combination of 7 SILAR cycles with 10% electrode solid content yielded the highest overall energy conversion efficiency. In particular this cell exhibited an outstanding open-circuit photovoltage up to 640 mV using a polysulfide electrolyte, which currently ranks the highest among reported literature. This outcome is due to the fact that a 10%-solid-content provided the largest pore sizes and the highest porosity for the QDs deposition, while the 7 SILAR cycles guaranteed the sufficient CdS QD loading which is favorable for light harvesting.

Ethynyl-linked push-pull porphyrin hetero-dimers for near-IR dye-sensitized solar cells: photovoltaic performances versus excited-state dynamics.

Ethynyl-linked porphyrin hetero-dimers substituted by a series of electron donors, namely, bis(4-methoxyphenyl)amino (BMPA), bis(4-tert-butylphenyl)amino (BTBPA) and 3,6-di-tert-butylcarbazol-9-yl (DTBC) as well as a reference dimer with a non-donor moiety (3,5-di-tert-butylphenyl, DTBP) have been synthesized to systematically investigate the influence of donor introduction on the photovoltaic performances of near-IR dye-sensitized solar cells (DSCs) with these sensitizers incorporated. Despite the expected bathochromic shift and intensification of long-wavelength absorption bands as well as elevated LUMO levels and thus increased electron injection driving forces, the substitution of diphenylamino groups (BMPA and BTBPA) with stronger electron-donating abilities gave rise to surprising mediocrity in the short-circuit photocurrent densities (J(sc)), leading to overall energy conversion efficiencies in the order BMPA (3.94%) < DTBP (4.57%) < BTBPA (4.83%) < DTBC (5.21%). A study of the in situ fluorescent behavior of these sensitizers revealed that for all the sensitizers, excited-state lifetimes were significantly shortened in the simulated DSC environment compared to those in a free solution. BMPA showed the shortest intrinsic in situ lifetime while DTBC showed the longest one. These results were correlated with the photovoltaic performances, which is required for a better understanding and further design of porphyrin array sensitizers.

Anionic structure-dependent photoelectrochemical responses of dye-sensitized solar cells based on a binary ionic liquid electrolyte.

Room temperature ionic liquids (RTILs) have been used as electrolytes to investigate the anionic structure dependence of the photoelectrochemical responses of dye-sensitized solar cells (DSCs). A series of RTILs with a fixed cation structure coupling with various anion structures are employed, in which 1-methyl-3-propylimidazolium iodide (PMII) and I(2) are dissolved as redox couples. It is found that both the diffusivity of the electrolyte and the photovoltaic performance of the device show a strong dependence on the fluidity of the ionic liquids, which is primarily altered by the anion structure. Further insights into the structure-dependent physical properties of the employed RTILs are discussed in terms of the reported van der Waals radius, the atomic charge distribution over the anion backbones, the interaction energy of the anion and cation, together with the existence of ion-pairs and ion aggregates. Particularly, both the short-circuit photocurrent and open-circuit voltage exhibit obvious fluidity dependence. Electrochemical impedance and intensity-modulated photovoltage/photocurrent spectroscopy analysis further reveal that increasing the fluidity of the ionic liquid electrolytes could significantly decrease the diffusion resistance of I(3)(-) in the electrolyte, and retard the charge recombination between the injected electrons with triiodide in the high-viscous electrolyte, thus improving the electron diffusion length in the device, as well as the photovoltaic response. However, the variation of the electron diffusion coefficients is trivial primarily due to the effective charge screening of the high cation concentration.

Bifunctional single-crystalline rutile nanorod decorated heterostructural photoanodes for efficient dye-sensitized solar cells.

A novel heterostructural TiO(2) nanocomposite, which consists of single-crystalline rutile TiO(2) nanorod decorated Degussa P25 nanoparticles, has been fabricated through a facile acidic hydrothermal method and successfully applied as the photoanodes for efficient dye-sensitized solar cells. The morphology, crystal structure, specific surface area and pore size distribution of the obtained nanocomposite were systematically investigated by X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), selected-area electron diffraction patterns (SAED) and nitrogen adsorption-desorption measurements. Under standard illumination conditions (AM 1.5, 100 mW cm(-2)), devices with these hybrid anodes exhibited considerably enhanced photocurrent density and overall conversion efficiency in comparison with that of the commercial Degussa P25 electrodes, which can be partially attributed to the light scattering effect in the long-wavelength region as evidenced from the incident photon-to-current conversion efficiency (IPCE) response and the diffuse reflectance spectroscopy. More importantly, devices employing these hybrid anodes have demonstrated extended electron lifetimes and larger electron diffusion coefficient as validated by the intensity-modulated photocurrent/photovoltage spectroscopy measurements, which can be mainly ascribed to the fast electron transport and collection superiority of the single-crystalline nanorods.