Pushing the heterometal doping limit while preserving long-lived charge separation in a Ti-based MOF photocatalyst.

This study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe3+-doped titanium-based metal organic framework (MOF), xFeMIL125-NH2, as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy. For each doping level, time-resolved X-ray transient absorption spectroscopy studies confirm the electron trap site role of the Fe sites in the excited state. Time scan data reveal multiexponential decay kinetics for the charge recombination processes which extend into the microsecond range for all three concentrations. A series of dye photodegradation studies, based on the oxidative decomposition of Rhodamine B, demonstrates the reactivity of the charge separated excited state and the photocatalytic capacity of these MOF materials compared to traditional heterometal-doped semiconductor photocatalysts.

Local Coordination and Electronic Structure Ramifications of Guest-Dependent Spin Crossover in a Metal-Organic Framework: A Combined X-ray Absorption and Emission Spectroscopy Study.

The porous Hoffman-type 3D lattice Fe(pz)[NiII(CN)4] exhibits thermally induced spin-crossover (SCO) behavior that is dependent on the solvent guest species occupying the pores. Here, in situ Fe K-edge X-ray absorption spectroscopy (XAS) and both non-resonant and resonant Kß X-ray emission spectroscopy (XES) methods are used to probe this framework under two solvent environments that yield different extremes of spin crossover temperature: acetonitrile and toluene. While the acetonitrile pore environment engenders an SCO response around room temperature, toluene guests stabilize the high spin state and effectively suppress SCO behavior throughout the ambient temperature range. The multipronged X-ray spectroscopy approach simultaneously confirmed this spin crossover behavior and provided new local coordination and electronic structural insights of the framework under these two solvent environments. Extended X-ray absorption fine structure analysis revealed spin state and solvent guest-dependent differences in coordination bond lengths and structural disorder. Resonant XES measurements produced high-resolution XAS spectra with distinct pre-edge and edge features, whose assignment was established using both simple ligand field theory and time-dependent density-functional theory calculations and further supported by their observed resonance behavior in the 2D RXES plane. Edge feature variation with the Fe spin state was interpreted to reveal changes in specific metal-linker bond covalency.

High resolution x-ray emission spectrometer for multiple hard x-ray emission lines: Demonstration for Cu Kα and Kß emissions.

We present a compact 3D printed x-ray emission spectrometer based on the von Hamos geometry that represents a significant upgrade to the existing von Hamos geometry-based miniature x-ray emission spectrometer (miniXES) [Mattern et al., Rev. Sci. Instrum. 83(2), 023901 (2012)]. The upgrades include the incorporation of a higher pixel density 500K detector for improved energy resolution and an enlarged sample area to accommodate a wider range of sample formats. The versatile spectrometer houses removable crystal holders that can be easily exchanged, as well as movable alignment eyelets that give flexibility in Bragg angle selection. Designed for ease of manufacture, all the components, except for the apertures, can be 3D printed and readily assembled. We describe its implementation in measurements of resonant and non-resonant Cu Kα and Kß x-ray emission and report the theoretical and measured energy resolution and collected solid angle of the emission.

Heterometal incorporation in NH2-MIL-125(Ti) and its participation in the photoinduced charge-separated excited state.

Optical and X-ray spectroscopy studies reveal the location and role of Fe3+ sites incorporated through direct synthesis in NH2-MIL-125(Ti). Fe K-edge XAS analysis confirms its metal-oxo cluster node coordination while time-resolved optical and X-ray transient absorption studies disclose its role as an electron trap site, promoting long-lived photo-induced charge separation in the framework. Notably, XTA measurements show sustained electron reduction of the Fe sites into the microsecond time range. Comparison with an Fe-doped MOF generated through post-synthetic modification indicates that only the direct synthesis approach affords efficient Fe participation in the charge separated excited state.

From IR to x-rays: gaining molecular level insights on metal-organic frameworks through spectroscopy.

This topical review focuses on the application of several types of spectroscopy methods to a class of solid state materials called metal organic frameworks (MOFs). MOFs are self-assembled, porous crystalline materials composed of metal cluster nodes linked through coordination bonds with organic or organometallic molecular constituents. Their unique host-guest properties make them attractive for many adsorption-based applications such as gas storage and separation, catalysis, sensing and others. While much research focuses on the development and application of these materials, fundamental studies of MOF properties and molecular level host-guest interactions behind their functionality have become a significant research direction on its own. Spectroscopy methods are now ubiquitous tools in this pursuit. This review focuses on the application of three classes of spectroscopy methods to MOF materials: vibrational, optical electronic and x-ray spectroscopies. Following brief introductions to each method that include pertinent theory and experimental considerations, we present a broad overview of the types of MOF systems that have been studied, with specific examples and important new molecular level insights highlighted along the way. The current status of spectroscopic studies of MOFs is presented at the end along with some perspectives on the future directions in this area of research.

Spectroscopic characterization of metal ligation in trinuclear iron-µ3-oxo-based complexes and metal-organic frameworks.

The adsorption-based functionalities of porous metal-organic framework (MOF) materials that lead to applications such as catalysis and gas separation rely on specific host-guest interactions often involving the framework metal sites. These interactions are difficult to probe on the molecular level and consequently poorly understood. Conventional X-ray absorption spectroscopy (XAS) methods can provide molecular-level insights but, as the sole method of characterization, often lack the ligand sensitivity required to probe the relevant local metal coordination changes associated with MOF adsorption processes. Here, we investigate a series of trinuclear iron µ3-oxo-based MOFs under different metal-coordinating guest environments (water, pyridine, propylene, and guest-free) using a multipronged spectroscopy approach, including valence-to-core X-ray emission spectroscopy (vtc-XES) along with conventional XAS and vibrational spectroscopy, in an effort to characterize their local metal site coordination environments, including ligand identity. Closely related iron µ3-oxo reference complexes with known coordination are characterized as well for comparison to evaluate the ligand diagnostic nature of the combined spectroscopy approach. Density functional theory calculations aid the vtc-XES band assignments and provide insights into the molecular orbital parentage of the vtc transitions. This series of MOFs and complexes illustrates the advantages and limitations of using this combination of complementary techniques for distinguishing subtle differences in framework metal node coordination environments.

Crystallographic identification of a series of manganese porphyrin complexes with nitrogenous bases.

Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme-based protein systems, but also the catalytic properties of porphyrin-based reaction sites in other biomimetic synthetic support environments. Unlike iron porphyrin complexes, little is known about the axial ligation behavior of Mn porphyrins, particularly in the solid state with Mn in the +3 oxidation state. Here, we present the syntheses and crystal and molecular structures of three new high-spin manganese(III) porphyrin complexes with the different amine-based axial ligands imidazole (im), piperidine (pip), and 1,4-diazabicyclo[2.2.2]octane (DABCO), namely bis(imidazole)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride chloroform disolvate, [Mn(C44H28N4)(C3H4N2)2]Cl·2CHCl3 or [Mn(TPP)(im)2]Cl·2CHCl3 (TPP = 5,10,15,20-tetraphenylporphyrin), (I), bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride, [Mn(C44H28N4)(C5H11N)2]Cl or [Mn(TPP)(pip)2]Cl, (II), and chlorido(1,4-diazabicyclo[2.2.2]octane)(5,10,15,20-tetraphenylporphyrin)manganese(III)-1,4-diazabicyclo[2.2.2]octane-toluene-water (4/4/4/1), [Mn(C44H28N4)Cl(C6H12N2)]·C6H12N2·C7H8·0.25H2O or [Mn(TPP)Cl(DABCO)]·(DABCO)·(toluene)·0.25H2O, (IV). A fourth complex, chlorido(pyridine)(5,10,15,20-tetraphenylporphryinato)manganese(III) pyridine disolvate, [Mn(C44H28N4)Cl(C5H5N)]·2C5H5N or [Mn(TPP)Cl(py)]·2(py), (III), acquired using different crystallization methods from published data, is also reported and compared to the previous structures.

Spectroscopic Evidence of Pore Geometry Effect on Axial Coordination of Guest Molecules in Metalloporphyrin-Based Metal Organic Frameworks.

A systematic comparison of host-guest interactions in two iron porphyrin-based metal-organic frameworks (MOFs), FeCl-PCN222 and FeCl-PCN224, with drastically different pore sizes and geometries is reported in this fundamental spectroscopy study. Guest molecules (acetone, imidazole, and piperidine) of different sizes, axial binding strengths, and reactivity with the iron porphyrin centers are employed to demonstrate the range of possible interactions that occur at the porphyrin sites inside the pores of the MOF. Binding patterns of these guest species under the constraints of the pore geometries in the two frameworks are established using multiple spectroscopy methods, including UV-vis diffuse reflectance, Raman, X-ray absorption, and X-ray emission spectroscopy. Line shape analysis applied to the latter method provides quantitative information on axial ligation through its spin state sensitivity. The observed coordination behaviors derived from the spectroscopic analyses of the two MOF systems are compared to those predicted using space-filling models and relevant iron porphyrin molecular analogues. While the space-filling models show the ideal axial coordination behavior associated with these systems, the spectroscopic results provide powerful insight into the actual binding interactions that occur in practice. Evidence for potential side reactions occurring within the pores that may be responsible for the observed deviation from model coordination behavior in one of the MOF/guest molecule combinations is presented and discussed in the context of literature precedent.

Spectroscopic Evidence for Room Temperature Interaction of Molecular Oxygen with Cobalt Porphyrin Linker Sites within a Metal-Organic Framework.

Metalloporphyrin-based metal-organic frameworks offer a promising platform for developing solid-state porous materials with accessible, coordinatively unsaturated metal sites. Probing small-molecule interactions at the metalloporphyrin sites within these materials on a molecular level under ambient conditions is crucial for both understanding and ultimately harnessing this functionality for potential catalytic purposes. Co-PCN-222, a metal-organic framework based on cobalt(II) porphyrin linkers. is investigated using in situ UV-vis diffuse-reflectance and X-ray absorption spectroscopy. Spectroscopic evidence for the axial interaction of diatomic oxygen with the framework's open metalloporphyrin sites at room temperature is presented and discussed.

Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced Iron-Porphyrin-Based Metal-Organic Framework.

An iron-porphyrin-based metal organic framework PCN-222(Fe) is investigated upon postsynthetic reduction with piperidine. Fe K-edge X-ray absorption and Kß mainline emission spectroscopy measurements reveal the local coordination geometry, oxidation, and spin state changes experienced by the Fe sites upon reaction with this axially coordinating reducing agent. Analysis and fitting of these data confirm the binding pattern predicted by a space-filling model of the structurally constrained pore environments. These results are further supported by UV-vis diffuse reflectance, IR, and resonance Raman spectroscopy data.

π-Plasmon absorption of carbon nanotubes for the selective and sensitive detection of Fe3+ ions.

Inspired by the remarkable electronic and optical properties of single walled carbon nanotubes (SWNTs), various molecular sensing devices with sensitivity down to the single molecule level have been developed. However, most sensing approaches such as field effect transistors or near infrared (NIR) fluorescence require the rigorous debundling and separation of metallic tubes and semiconducting tubes in order to reach the desired high sensitivity. Interestingly, all carbon nanomaterials including carbon nanotubes, graphite, graphene, and even amorphous carbon exhibit extremely strong π-plasmon absorption in the ultraviolet region. This strong absorption has been studied as an undesired optical background for applications based on visible and NIR absorptions. For the first time, we found that the strong π-plasmon absorption of SWNTs in the ultraviolet region is extremely sensitive to ion binding. It is even much more sensitive than the absorption in the visible and NIR regions. Herein, we present our first exploration into using the extremely strong plasmon absorption of SWNTs to develop a new sensing platform for the detection of metallic ions. The detection selectivity is realized by modifying the surface of SWNTs with molecular ligands that have a high specificity for metal ions. As a demonstration, the new method is applied to selectively detect iron ions (Fe3+) by modifying the surface of the SWNTs with deferoxamine (DFO), a natural bacterial siderophore, which has a high specificity and affinity for Fe3+. The selective detection of Fe3+ in both aqueous solution and complex rain water is achieved with a pM level of sensitivity and detection limit. In situ resonant Raman spectroscopy demonstrated that the sensitive detection possibly involves electron transfer between the formed Fe-DFO complexes and the SWNTs. We envisage that it can be used to detect other metal ions when a specific binding chelator is attached to the carbon nanotube surface.

Privileged phosphine-based metal-organic frameworks for broad-scope asymmetric catalysis.

A robust and porous Zr metal-organic framework (MOF) based on a BINAP-derived dicarboxylate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantioselective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantioselective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP precatalysts with the same coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to α,ß-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.

Detailed transient heme structures of Mb-CO in solution after CO dissociation: an X-ray transient absorption spectroscopic study.

Although understanding the structural dynamics associated with ligand photodissociation is necessary in order to correlate structure and function in biological systems, few techniques are capable of measuring the ultrafast dynamics of these systems in solution-phase at room temperature. We present here a detailed X-ray transient absorption (XTA) study of the photodissociation of CO-bound myoglobin (Fe(II)CO-Mb) in room-temperature aqueous buffer solution with a time resolution of 80 ps, along with a general procedure for handling biological samples under the harsh experimental conditions that transient X-ray experiments entail. The XTA spectra of (Fe(II)CO-Mb) exhibit significant XANES and XAFS alterations following 527 nm excitation, which remain unchanged for >47 µs. These spectral changes indicate loss of the CO ligand, resulting in a five-coordinate, domed heme, and significant energetic reorganization of the 3d orbitals of the Fe center. With the current experimental setup, each X-ray pulse in the pulse train, separated by ~153 ns, can be separately discriminated, yielding snapshots of the myoglobin evolution over time. These methods can be easily applied to other biological systems, allowing for simultaneous structural and electronic measurements of any biological system with both ultrafast and slow time resolutions, effectively mapping out all of the samples' relevant physiological processes.

Ground-state and excited-state structures of tungsten-benzylidyne complexes.

The molecular structure of the tungsten-benzylidyne complex trans-W(≡CPh)(dppe)(2)Cl (1; dppe = 1,2-bis(diphenylphosphino)ethane) in the singlet (d(xy))(2) ground state and luminescent triplet (d(xy))(1)(π*(WCPh))(1) excited state (1*) has been studied using X-ray transient absorption spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Molecular-orbital considerations suggest that the W-C and W-P bond lengths should increase in the excited state because of the reduction of the formal W-C bond order and decrease in W→P π-backbonding, respectively, between 1 and 1*. This latter conclusion is supported by comparisons among the W-P bond lengths obtained from the X-ray crystal structures of 1, (d(xy))(1)-configured 1(+), and (d(xy))(2) [W(CPh)(dppe)(2)(NCMe)](+) (2(+)). X-ray transient absorption spectroscopic measurements of the excited-state structure of 1* reveal that the W-C bond length is the same (within experimental error) as that determined by X-ray crystallography for the ground state 1, while the average W-P/W-Cl distance increases by 0.04 Å in the excited state. The small excited-state elongation of the W-C bond relative to the M-E distortions found for M(≡E)L(n) (E = O, N) compounds with analogous (d(xy))(1)(π*(ME))(1) excited states is due to the π conjugation within the WCPh unit, which lessens the local W-C π-antibonding character of the π*(WCPh) lowest unoccupied molecular orbital (LUMO). These conclusions are supported by DFT calculations on 1 and 1*. The similar core bond distances of 1, 1(+), and 1* indicates that the inner-sphere reorganization energy associated with ground- and excited-state electron-transfer reactions is small.

Strong steric hindrance effect on excited state structural dynamics of Cu(I) diimine complexes.

The metal-to-ligand-charge-transfer (MLCT) excited state of Cu(I) diimine complexes is known to undergo structural reorganization, transforming from a pseudotetrahedral D(2d) symmetry in the ground state to a flattened D(2) symmetry in the MLCT state, which allows ligation with a solvent molecule, forming an exciplex intermediate. Therefore, the structural factors that influence the coordination geometry change and the solvent accessibility to the copper center in the MLCT state could be used to control the excited state properties. In this study, we investigated an extreme case of the steric hindrance caused by attaching bulky tert-butyl groups in bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I), [Cu(I)(dtbp)(2)](+). The two bulky tert-butyl groups on the dtbp ligand lock the MLCT state into the pseudotetrahedral coordination geometry and completely block the solvent access to the copper center in the MLCT state of [Cu(I)(dtbp)(2)](+). Using ultrafast transient absorption spectroscopy and time-resolved emission spectroscopy, we investigated the MLCT state property changes due to the steric hindrance and demonstrated that [Cu(I)(dtbp)(2)](+) exhibited a long-lived emission but no subpicosecond component that was previously assigned as the flattening of the pseudotetrahedral coordination geometry. This suggests the retention of its pseudotetrahedral D(2d) symmetry and the blockage of the solvent accessibility. We made a comparison between the excited state dynamics of [Cu(I)(dtbp)(2)](+) with its mono-tert-butyl counterpart, bis(2-tert-butyl-1,10-phenanthroline)copper(I) [Cu(I)(tbp)(2)](+). The subpicosecond component assigned to the flattening of the D(2d) coordination geometry in the MLCT excited state was again present in the latter because the absence of a tert-butyl on the phenanthroline allows flattening to the pseudotetrahedral coordination geometry. Unlike the [Cu(I)(dtbp)(2)](+), [Cu(I)(tbp)(2)](+) exhibited no detectable emission at room temperature in solution. These results provide new insights into the manipulation of various excited state properties in Cu diimine complexes by certain key structural factors, enabling optimization of these systems for solar energy conversion applications.

Coherence in metal-metal-to-ligand-charge-transfer excited states of a dimetallic complex investigated by ultrafast transient absorption anisotropy.

Coherence in the metal-metal-to-ligand-charge transfer (MMLCT) excited state of diplatinum molecule [Pt(ppy)(µ-(t)Bu(2)pz)](2) has been investigated through the observed oscillatory features and their corresponding frequencies as well as polarization dependence in the single-wavelength transient absorption (TA) anisotropy signals. Anticorrelated parallel and perpendicular TA signals with respect to the excitation polarization direction were captured, while minimal oscillatory features were observed in the magic angle TA signal. The combined analysis of the experimental results coupled with those previous calculated in the literature maps out a plausible excited state trajectory on the potential energy surface, suggesting that (1) the two energetically close MMLCT excited states due to the symmetry of the molecule may be electronically and coherently coupled with the charge density shifting back and forth between the two phenylpyridine (ppy) ligands, (2) the electronic coupling strength in the (1)MMLCT and (3)MMLCT states may be extracted from the oscillation frequencies of the TA signals to be 160 and 55 cm(-1), respectively, (3) a stepwise intersystem crossing cascades follows (1)MMLCT → (3)MMLCT (T(1b)) → (3)MMLCT (T(1a)), and (4) a possible electronic coherence can be modulated via the Pt-Pt σ-interactions over a picosecond and survive the first step of intersystem crossing. Future experiments are in progress to further investigate the origin of the oscillatory features. These experimental observations may have general implications in design of multimetal center complexes for photoactivated reactions where coherence in the excited states may facilitate directional charge or energy transfer along a certain direction between different parts of a molecule.

Triplet excited state distortions in a pyrazolate bridged platinum dimer measured by X-ray transient absorption spectroscopy.

The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(µ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed.

Faster interprotein electron transfer in a [myoglobin, b5] complex with a redesigned interface.

Direct measurements of electron transfer (ET) within a protein-protein complex with a redesigned interface formed by physiological partner proteins myoglobin (Mb) and cytochrome b(5) (b(5)) reveal interprotein ET rates comparable to those observed within the photosynthetic reaction center. Brownian dynamics simulations show that Mb in which three surface acid residues are mutated to lysine binds b(5) in an ensemble of configurations distributed around a reactive most-probable structure. Correspondingly, charge-separation ET from a photoexcited singlet zinc porphyrin incorporated within Mb to the heme of b(5) and the follow-up charge-recombination exhibit distributed kinetics, with median rate constants, k(f)(s) = 2.1 × 10(9) second(-1) and k(b)(s) = 4.3 × 10(10) second(-1), respectively. The latter approaches that for the initial step in photosynthetic charge separation, k = 3.3 × 10(11) second(-1).

Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes.

This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of Cu(I) diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1,10-phenanthroline) [Cu(I)(detp)(2)](+) are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)bis(1,10-phenanthroline), [Cu(I)(phen)(2)](+), and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [Cu(I)(dmp)(2)](+), model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [Cu(I)(detp)(2)](+) and [Cu(I)(phen)(2)](+) excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [Cu(I)(detp)(2)](+), [Cu(I)(phen)(2)](+), and [Cu(I)(dmp)(2)](+) are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.

Narrow-bandwidth tunable picosecond pulses in the visible produced by noncollinear optical parametric amplification with a chirped blue pump.

Narrow-bandwidth (approximately 27 cm(-1)) tunable picosecond pulses from 480 nm-780 nm were generated from the output of a 1 kHz femtosecond titanium:sapphire laser system using a type I noncollinear optical parametric amplifier (NOPA) with chirped second-harmonic generation (SHG) pumping. Unlike a femtosecond NOPA, this system utilizes a broadband pump beam, the chirped 400 nm SHG of the Ti:sapphire fundamental, to amplify a monochromatic signal beam (spectrally-filtered output of a type II collinear OPA). Optimum geometric conditions for simultaneous phase- and group-velocity matching were calculated in the visible spectrum. This design is an efficient and simple method for generating tunable visible picosecond pulses that are synchronized to the femtosecond pulses.