Identification of vanadium dopant sites in the metal-organic framework DUT-5(Al).

Studying the structural environment of the VIV ions doped in the metal-organic framework (MOF) DUT-5(Al) ((AlIIIOH)BPDC) with electron paramagnetic resonance (EPR) reveals four different vanadium-related spectral components. The spin-Hamiltonian parameters are derived by analysis of X-, Q- and W-band powder EPR spectra. Complementary Q-band Electron Nuclear DOuble Resonance (ENDOR) experiments, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX), X-Ray Diffraction (XRD) and Fourier Transform InfraRed (FTIR) measurements are performed to investigate the origin of these spectral components. Two spectral components with well resolved 51V hyperfine structure are visible, one corresponding to VIV[double bond, length as m-dash]O substitution in a large (or open) pore and one to a narrow (or closed) pore variant of this MOF. Furthermore, a broad structureless Lorentzian line assigned to interacting vanadyl centers in each other's close neighborhood grows with increasing V-concentration. The last spectral component is best visible at low V-concentrations. We tentatively attribute it to (VIV[double bond, length as m-dash]O)2+ linked with DMF or dimethylamine in the pores of the MOF. Simulations using these four spectral components convincingly reproduce the experimental spectra and allow to estimate the contribution of each vanadyl species as a function of V-concentration.

Nitrogen-vacancy nanodiamond based local thermometry using frequency-jump modulation.

A straightforward and sensitive approach is presented for contact-free thermal sensing with high spatial resolution based on optically detected magnetic resonance (ODMR) of negatively charged nitrogen-vacancy (NV) centers in fluorescent nanodiamonds. The frequency-jump procedure is a frequency modulation technique between two discrete frequencies at the inflection points at both sides of the NV ODMR resonance, which yields a signal proportional to the temperature shift over a wide temperature range. The approach is generic and is demonstrated by time-dependent measurements of the local temperature at different spots on a microelectronics circuit under electrical switching operation of one of the devices.

Impact of the donor polymer on recombination via triplet excitons in a fullerene-free organic solar cell.

The greater chemical tunability of non-fullerene acceptors enables fine-tuning of the donor-acceptor energy level offsets, a promising strategy towards increasing the open-circuit voltage in organic solar cells. Unfortunately, this approach could open an additional recombination channel for the charge-transfer (CT) state via a lower-lying donor or acceptor triplet level. In this work we investigate such electron and hole back-transfer mechanisms in fullerene-free solar cells incorporating the novel molecular acceptor 2,4-diCN-Ph-DTTzTz. The transition to the low-driving force regime is studied by comparing blends with well-established donor polymers P3HT and MDMO-PPV, which allows for variation of the energetic offsets at the donor-acceptor interface. Combining various optical spectroscopic techniques, the CT process and subsequent triplet formation are systematically investigated. Although both back-transfer mechanisms are found to be energetically feasible in both blends, markedly different triplet-mediated recombination processes are observed for the two systems. The kinetic suppression of electron back-transfer in the blend with P3HT suggests that energy losses due to triplet formation on the polymer can be avoided, regardless of favorable energetic alignment.

Sensing the framework state and guest molecules in MIL-53(Al) via the electron paramagnetic resonance spectrum of VIV dopant ions.

X-ray diffraction (XRD) and electron paramagnetic resonance spectroscopy (EPR) were combined to study the structural transformations induced by temperature, pressure and air humidity of the "breathing" metal-organic framework (MOF) MIL-53(Al), doped with paramagnetic VIV ions, after activation. The correlation between in situ XRD and thermogravimetric analysis measurements showed that upon heating this MOF in air, starting from ambient temperature and pressure, the narrow pore framework first dehydrates and after that makes the transition to a large pore state (lp). The EPR spectra of VIV[double bond, length as m-dash]O molecular ions, replacing Al-OH in the structure, also allow to distinguish the as synthesized, hydrated (np-h) and dehydrated narrow pore (np-d), and lp states of MIL-53(Al). A careful analysis of EPR spectra recorded at microwave frequencies between 9.5 and 275 GHz demonstrates that all VIV[double bond, length as m-dash]O in the np-d and lp states are equivalent, whereas in the np-h state (at least two) slightly different VIV[double bond, length as m-dash]O sites exist. Moreover, the lp MIL-53(Al) framework is accessible to oxygen, leading to a notable broadening of the VIV[double bond, length as m-dash]O EPR spectrum at pressures of a few mbar, while such effect is absent for the np-h and np-d states for pressures up to 1 bar.

Molecular orientation of lead phthalocyanine on (100) oriented single crystal diamond surfaces.

Lead phthalocyanine (PbPc) thin films of 5 and 50 nm have been deposited on hydrogen and oxygen terminated single crystal diamond (SCD) using organic molecular beam deposition. Atomic force microscopy and X-ray diffraction (XRD) studies showed that PbPc grown on the hydrogen terminated SCD forms layers with a high degree of crystallinity, dominated by the monoclinic (320) orientation parallel to the diamond surface. The oxygen terminated diamond led to a randomly oriented PbPc film. Absorption and photocurrent measurements indicated the presence of both polymorphs of PbPc, however, the ratio differed depending on the termination of the SCD. Finally, polarized Raman spectroscopy was used to determine the orientation of the molecules of the thin film. The results confirmed the random orientation on the O-terminated diamond. On SCD:H, the PbPc molecules are lying down in accordance with the XRD results.

Electronic structure of positive and negative polarons in functionalized dithienylthiazolo[5,4-d]thiazoles: a combined EPR and DFT study.

2,5-Dithienylthiazolo[5,4-d]thiazole (DTTzTz) derivatives have high potential for solution-processed organic field-effect transistors and solar cells, both as electron acceptors and donors. Here, the electronic structure of positive and negative radicals (polarons) of two functionalized DTTzTz materials is studied using multi-frequency and multi-resonance electron paramagnetic resonance (EPR) in combination with density functional theory (DFT). It is shown that the negative and positive DTTzTz polarons can be distinguished on the basis of their characteristic EPR parameters. The chemically induced polarons are compared to light-generated states observed in a blend of one of the DTTzTz derivatives with a donor polymer. The study gives in-depth information about the spread of the electron or hole in the DTTzTz molecules.

Chirality Dependence of Triplet Excitons in (6,5) and (7,5) Single-Wall Carbon Nanotubes Revealed by Optically Detected Magnetic Resonance.

The excitonic structure of single-wall carbon nanotubes (SWCNTs) is chirality dependent and consists of multiple singlet and triplet excitons (TEs) of which only one singlet exciton (SE) is optically bright. In particular, the dark TEs have a large impact on the integration of SWCNTs in optoelectronic devices, where excitons are created electrically, such as in infrared light-emitting diodes, thereby strongly limiting their quantum efficiency. Here, we report the characterization of TEs in chirality-purified samples of (6,5) and (7,5) SWCNTs, either randomly oriented in a frozen solution or with in-plane preferential orientation in a film, by means of optically detected magnetic resonance (ODMR) spectroscopy. In both chiral structures, the nanotubes are shown to sustain three types of TEs. One TE exhibits axial symmetry with zero-field splitting (ZFS) parameters depending on SWCNT diameter, in good agreement with the tighter confinement expected in narrower-diameter nanotubes. The ZFS of this TE also depends on nanotube environment, pointing to slightly weaker confinement for surfactant-coated than for polymer-wrapped SWCNTs. A second TE type, with much smaller ZFS, does not show the same systematic trends with diameter and environment and has a less well-defined axial symmetry. This most likely corresponds to TEs trapped at defect sites at low temperature, as exemplified by comparing SWCNT samples from different origins and after different treatments. A third triplet has unresolved ZFS, implying it originates from weakly interacting spin pairs. Aside from the diameter dependence, ODMR thus provides insights in both the symmetry, confinement, and nature of TEs on semiconducting SWCNTs.

Charge transfer in the weak driving force limit in blends of MDMO-PPV and dithienylthiazolo[5,4-d]thiazoles towards organic photovoltaics with high V(OC).

A series of three 5'-aryl-2,5-dithienylthiazolo[5,4-d]thiazole (DTTzTz) semiconducting molecules with different aryl substituents has been investigated as alternative acceptor materials in combination with the donor polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) in order to evaluate the photoinduced charge transfer (CT) efficiency in the resulting blends, designed towards possible application in organic photovoltaics. Photoluminescence quenching together with polaron detection by electron paramagnetic resonance and photoinduced absorption (PIA) demonstrate an increasing charge transfer efficiency when the DTTzTz substituents are varied from thien-2-yl to 4-trifluoromethylphenyl and 4-cyanophenyl groups, correlating well with the increasing acceptor strength in this series of molecules. In line with this observation, there is a decrease in the effective optical bandgap relative to pure MDMO-PPV that becomes more pronounced along this series of acceptor compounds, reaching 0.12 eV in the blend with 4-CN-Ph-DTTzTz. Intermolecular interactions between the blend components lead to lower energy transitions which are found to contribute significantly to the device external quantum efficiency. The high V(OC) reached in devices based on MDMO-PPV:4-CN-Ph-DTTzTz blends meets the expectations for such a donor:acceptor combination. However, thermal activation of charge carrier recombination occurs because of the weak driving force for charge transfer, as shown by time-dependent PIA measurements, and this is suggested as a cause for the observed low photovoltaic performance.

W-band transient EPR and photoinduced absorption on spin-labeled fullerene derivatives.

We investigated by W-band (94 GHz) transient electron paramagnetic resonance (TREPR) and photoinduced absorption (PIA) spectroscopy two fullerene derivatives bearing a nitroxide radical unit. After pulsed laser photoexcitation of the molecules in liquid toluene solution, complex EPR spectra are recorded, with lines in absorption and emission. The intrinsic higher spectral and temporal resolution of the W-band frequency leads to the assignment of all the lines in the spectrum and the determination of the sign and the absolute value of the exchange coupling between the fullerene in its photoexcited triplet state (S(T) = 1) and the radical (S(R) = 1/2). The two compounds with different fullerene-nitroxide spacers show opposite-ferromagnetic and antiferromagnetic-exchange couplings. The time evolution of the spectra and the polarization of the lines are interpreted in terms of several possible spin polarization mechanisms. The EPR measurements are complemented with PIA experiments.

The solid-state organization of 'self-doped' PPV oligomers.

Using a combination of multi-frequency EPR and NMR spectroscopy and quantum-chemical calculations at the level of Density Functional Theory (DFT), the organization of self-doped PPV oligomers in their solid state is investigated. The analysis of the different spectra shows that the electrochemical procedure used to self-dope these materials produces positive radicals (polarons) in an almost quantitative way, but still magnetically isolated polarons are observed. The difference between chemical and electrochemical oxidation of the oligomers is studied in detail. Furthermore, ageing of the electrochemically oxidized oligomers may be accompanied by a stacking of the oligomers.

First hyperpolarizability dispersion of the octupolar molecule crystal violet: multiple resonances and vibrational and solvation effects.

The first hyperpolarizability (ß) dispersion curve is measured for the first time for an octupolar nonlinear optical (NLO) molecule (crystal violet, CV) and modeled theoretically, yielding an in-depth understanding of the electronic structure and vibronic and solvation effects on such octupolar conjugated systems. Tunable wavelength hyper-Rayleigh scattering (HRS) measurements were performed on this prototypical octupolar molecule in the broad fundamental wavelength range of 620-1580 nm, showing significant shortcomings of the commonly used ß dispersion models. Three well-separated ß resonances involving the lowest-energy state and several higher excited states are clearly observed, including a significant contribution from a nominally one-photon forbidden transition. The experimental results for second-harmonic wavelengths above 330 nm are successfully modeled by means of a vibronically coupled essential-state description for octupolar chromophores, developed by Terenziani et al. (J. Phys. Chem. B 2008, 112, 5079), which takes into account polar solvation effects. The relative intensities of the various resonances, including the one below 330 nm, are also quantified by quantum chemical calculations. Furthermore, interesting effects of inhomogeneous broadening due to polar solvation of the two-dimensional chromophore are recognized in both linear and nonlinear spectra, allowing us to quantitatively address the long-standing problem of the band shape of the linear absorption spectrum of CV. This clearly demonstrates that extensive wavelength-dependent HRS measurements, as presented in this work, are essential to the characterization and design of NLO materials and represent a powerful tool to gain valuable information on molecular excitations and environmental effects in general.

Experimental observation of single-file water filling of thin single-wall carbon nanotubes down to chiral index (5,3).

Single-file transport of water into carbon nanotubes is experimentally demonstrated for the first time through the splitting of the radial breathing mode (RBM) vibration in Raman spectra of bile salt solubilized tubes when both empty (closed) and water-filled (open-ended) tubes are present. D2O filling is observed for a wide range of diameters, d, down to very thin tubes [e.g., (5,3) tube, d=0.548 nm] for which only a single water molecule fits in the cross section of the internal nanotube channel. The shift in RBM frequency upon filling is found to display a very complex dependence on nanotube diameter and chirality, in support of a different yet well-defined ordering and orientation of water molecules at room temperature. Large shifts of the electronic transitions are also observed.

Highly sensitive setup for tunable wavelength hyper-Rayleigh scattering with parallel detection and calibration data for various solvents.

A very sensitive experimental setup for accurate wavelength-dependent hyper-Rayleigh scattering (HRS) measurements of the molecular first hyperpolarizability beta in the broad fundamental wavelength range of 600 to 1800 nm is presented. The setup makes use of a stable continuously tunable picosecond optical parametric amplifier with kilohertz repetition rate. To correct for multi-photon fluorescence, a small spectral range around the second harmonic wavelength is detected in parallel using a spectrograph coupled to an intensified charge-coupled device. Reliable calibration against the pure solvent is possible over the full accessible spectral range. An extensive set of wavelength-dependent HRS calibration data for a wide range of solvents is presented, and very accurate measurements of the beta dispersion of the well-known nonlinear optical chromophore Disperse Red 1 are demonstrated.

Characterisation of nanohybrids of porphyrins with metallic and semiconducting carbon nanotubes by EPR and optical spectroscopy.

Single-walled carbon nanotubes (SWCNTs) are noncovalently functionalised with octaethylporphyrins (OEPs) and the resulting nanohybrids are isolated from the free OEPs. Electron paramagnetic resonance (EPR) spectroscopy of cobalt(II)OEP, adsorbed on the nanotube walls by pi-pi-stacking, demonstrates that the CNTs act as electron acceptors. EPR is shown to be very effective in resolving the different interactions for metallic and semiconducting tubes. Moreover, molecular oxygen is shown to bind selectively to nanohybrids with semiconducting tubes. Water solubilisation of the porphyrin/CNT nanohybrids using bile salts, after applying a thorough washing procedure, yields solutions in which at least 99% of the porphyrins are interacting with the CNTs. Due to this purification, we observe, for the first time, the isolated absorption spectrum of the interacting porphyrins, which is strongly red-shifted compared to the free porphyrin absorption. In addition a quasi-complete quenching of the porphyrin fluorescence is also observed.

Disentangling overlapping high-field EPR spectra of organic radicals: Identification of light-induced polarons in the record fullerene-free solar cell blend PBDB-T:ITIC.

We present a combined high-field EPR and DFT study of light-induced radicals in the bulk heterojunction blend of PBDB-T:ITIC, currently one of the highest efficiency non-fullerene donor:acceptor combinations in organic photovoltaics. We demonstrate two different approaches for disentangling the strongly overlapping high-field EPR spectra of the positive and negative polarons after charge separation: (1) relaxation-filtered field-swept EPR based on the difference in T1 spin-relaxation times and (2) field-swept EDNMR-induced EPR by exploiting the presence of 14N hyperfine couplings in only one of the radical species, the small molecule acceptor radical. The approach is validated by light-induced EPR spectra on related blends and the spectral assignment is underpinned by DFT computations. The broader applicability of the spectral disentangling methods is discussed.

Multifrequency electron paramagnetic resonance study on deproteinized human bone.

Irradiated samples of deproteinized powdered human bone (femur) have been examined by electron paramagnetic resonance (EPR) spectroscopy in X, Q and W bands. In the bone powder sample only one type of CO2- radical ion is stabilized in the hydroxyapatite structure in contrast to powdered human tooth enamel, a material also containing hydroxyapatite, widely used for EPR dosimetry and in which a few radicals are stable at room temperature. It is suggested that the use of deproteinized bone for EPR dosimetry could improve the accuracy of dose determination.

Single-ion and molecular contributions to the zero-field splitting in an iron(III)-oxo dimer studied by single crystal W-band EPR.

Detailed knowledge of the type and strength of pair interactions between high-spin metal ions is paramount to the understanding and design of molecular magnetic materials. In this work, the anisotropic magnetic interactions in a beta-diketonate-alkoxide iron(III) dimer compound, [Fe2(OCH3)2(dbm)4, Hdbm=dibenzoylmethane] (Fe2) have been investigated by single crystal electron paramagnetic resonance (EPR) in the W-band (at 95GHz). The diamagnetic substitution method was employed using the isomorphous gallium(III)-based compound doped with iron(III) to produce Ga-Fe dimers (GaFe). The single-ion zero-field splitting (ZFS) tensor could be separately determined in GaFe with the iron ion in a local environment quasi-identical to the one in Fe2. Its principal directions are found to point in arbitrary directions, uncorrelated with the Fe-O bonds. The Fe2 EPR spectra consist of transitions within the lowest multiplet states S=1,2,3, which were analyzed using the full spin Hamiltonian description of an exchange coupled pair of s=5/2 spins. The anisotropic spin-spin interaction tensor of Fe2 possesses a principal axis close to the Fe-Fe direction and was shown to arise both from through-space (dipolar) and through-bond (anisotropic exchange) contributions. The latter involves an rhombic component JE=(JX-JY)/2 approximately 0.093 cm-1 of magnitude comparable to the dipolar interaction, and even to the rhombic part of the single-ion ZFS (E=0.097 cm-1). Our results show that the anisotropic exchange, usually neglected for S-type ions, is significant for the anisotropic interactions in exchange-coupled iron(III) clusters, including the Fe4 and Fe8 families of single-molecule magnets and the antiferromagnetic iron wheels.

Revealing the Cu(2+) ions localization at low symmetry Bi sites in photorefractive Bi12GeO20 crystals doped with Cu and V by high frequency EPR.

The sites of incorporation of Cu(2+) impurity ions in Bi12GeO20 single crystals co-doped with copper and vanadium have been investigated by electron paramagnetic resonance (EPR). While the X-band EPR spectra consist of a simple broad (ΔB ∼50 mT) line with anisotropic lineshape, the W-band EPR spectra exhibit well resolved, strongly anisotropic lines, due to transitions within the 3d(9)-(2)D ground manifold of the Cu(2+) ions. The most intense group of lines, attributed to the dominant Cu(2+)(I) center, displays a characteristic four components hyperfine structure for magnetic field orientations close to a 〈110〉 direction. The g and A tensor main axes are very close to one of the 12 possible sets of orthogonal 〈1-10〉, 〈00-1〉 and 〈110〉 crystal directions. Several less intense lines, with unresolved hyperfine structure and similar symmetry properties, mostly overlapped by the Cu(2+)(I) spectrum, were attributed to Cu(2+)(II) centers. The two paramagnetic centers are identified as substitutional Cu(2+) ions at Bi(3+) sites with low C1 symmetry, very likely resulting from different configurations of neighboring charge compensating defects.

Complexation properties of N-thiophosphorylated thiourea 2-PyNHC(S)NHP(S)(OiPr)2 towards Ni(II).

Reaction of the deprotonated N-thiophosphorylated thiourea 2-PyNHC(S)NHP(S)(OiPr)2 (HL) with NiCl2 leads to the complex [Ni{2-PyNHC(S)NP(S)(OiPr)2}2] ([NiL2]) with unprecedented 1,5,7-N,N',S-coordination of the ligand. Recrystallization of [NiL2] from a mixture of CH2Cl2­n-hexane or acetone­n-hexane leads to [Ni(L-1,5,7-N,N',S)2]·CH2Cl2 and [Ni(L-1,5,7-N,N',S)2], respectively. The latter complex, in turn, shows a temperature-induced polymorphism. [NiL2] in solution shows a paramagnetic distorted octahedral structure where the metal center is coordinated through the nitrogen atoms of the phosphorylamide and pyridyl group functions, and oxygen atoms of the phosphorylamide unit. Furthermore, in the solid state at low temperature, [Ni(L-1,5,7-N,N',S)2] is shown from high-frequency EPR measurements to possess an S = 1 ground state with large anisotropy.

Determination of the metallic/semiconducting ratio in bulk single-wall carbon nanotube samples by cobalt porphyrin probe electron paramagnetic resonance spectroscopy.

A simple and quantitative, self-calibrating spectroscopic technique for the determination of the ratio of metallic to semiconducting single-wall carbon nanotubes (SWCNTs) in a bulk sample is presented. The technique is based on the measurement of the electron paramagnetic resonance (EPR) spectrum of the SWCNT sample to which cobalt(II)octaethylporphyrin (CoOEP) probe molecules have been added. This yields signals from both CoOEP molecules on metallic and on semiconducting tubes, which are easily distinguished and accurately characterized in this work. By applying this technique to a variety of SWCNT samples produced by different synthesis methods, it is shown that these signals for metallic and semiconducting tubes are independent of other factors such as tube length, defect density, and diameter, allowing the intensities of both signals for arbitrary samples to be retrieved by a straightforward least-squares regression. The technique is self-calibrating in that the EPR intensity can be directly related to the number of spins (number of CoOEP probe molecules), and as the adsorption of the CoOEP molecules is itself found to be unbiased toward metallic or semiconducting tubes, the measured intensities can be directly related to the mass percentage of metallic and semiconducting tubes in the bulk SWCNT sample. With the use of this method it was found that for some samples the metallic/semiconducting ratios strongly differed from the usual 1:2 ratio.