How complex-surface interactions modulate the spin transition of Fe(II) SCO complexes supported on metallic surfaces?

The deposition of a prototypical spin-crossover [Fe(phen)2(NCS)2] complex on Au(111), Cu(111) and Ag(111) surfaces has been investigated by means of periodic DFT+U calculations, with the aim of understanding how different metallic surfaces affect the spin state switching. Our results show that adsorption is metal- and spin-dependent, with different preferred adsorption sites for the different surfaces and spin states. For the three considered surfaces adsorption energies are larger in the LS state than in the HS one, which increases the transition enthalpy by 58.7 kJ mol-1 for Cu(111), 14.6 kJ mol-1 for Au(111) and 9.6 kJ mol-1 for Ag(111) with respect to the free molecule. There is a clear correlation between this effect and the extent of the complex-surface interaction, which can be established from adsorption energies, surface-complex distances and charge density difference plots as: Cu(111) > Au(111) > Ag(111). Therefore, a stronger interaction with the surface produces a larger energy difference between two spin states, making the spin transition less probable to occur. Finally, our calculations show that it would be possible to probe the spin-state of the deposited molecules from the STM images, in line with the recent experimental results.

Spin-crossover complexes in nanoscale devices: main ingredients of the molecule-substrate interactions.

Spin-crossover complexes embedded in nanodevices experience effects that are absent in the bulk that can modulate, quench and even suppress the spin-transition. In this work we explore, by means of state-of-the-art quantum chemistry calculations, different aspects of the integration of SCO molecules on active nanodevices, such as the geometry and energetics of the interaction with the substrate, extension of the charge transfer between the substrate and SCO molecule, impact of the applied external electric field on the spin-transition, and sensitivity of the transport properties on the local conditions of the substrate. We focus on the recently reported encapsulation of Fe(II) spin-crossover complexes in single-walled carbon nanotubes, with new measurements that support the theoretical findings. Even so our results could be useful to many other systems where SCO phenomena take place at the nanoscale, the spin-state switching is probed by an external electric field or current, or the substrate is responsible for the quenching of the SCO mechanism.

A photo-induced spin crossover based molecular switch and spin filter operating at room temperature.

Since Venkataramani et al. (Science, 2011, 331(6016), 445-448) reported reversible, room-temperature light-induced spin crossover in Ni-porphyrin functionalized with a phenylazopyridine ligand (NiTPP-PAPy), this complex has attracted the attention of many researchers due to its potential applications in molecular-based devices. In this work, we perform a detailed study, by means of DFT and WFT methodologies, focused on the deposition of NiTP-PAPy over an Au(111) surface, followed by DFT-NEGF calculations employing a gold surface and the tip of an STM as electrodes, in order to probe the deposited complex's transport properties. Our DFT calculations show that not only the metalled porphyrin is strongly adsorbed on the surface, in both the high (HS) and low spin (LS) configurations, but also, and more importantly, photoinduced switching is preserved upon adsorption, a fact that is also confirmed through WFT and TD-DFT calculations. Moreover, our DFT-NEGF calculations indicate that the current passing through the molecular junction-like systems is much higher in the HS configuration than in the LS one, along with the fact that the current calculated in the ferromagnetic junction is highly spin-polarized. These remarkable transport properties suggest that the complex could be used as a component in molecular switches based on the total current passing through the system, modulated by light irradiation, spin filters due to the spin polarization of the carriers in the HS configuration, or even in two-step rectifiers combining the two features mentioned above, all of these operating at room temperature, giving to this complex the potential to be an active element in all kinds of future spintronic devices.

Spin-state-dependent electrical conductivity in single-walled carbon nanotubes encapsulating spin-crossover molecules.

Spin crossover (SCO) molecules are promising nanoscale magnetic switches due to their ability to modify their spin state under several stimuli. However, SCO systems face several bottlenecks when downscaling into nanoscale spintronic devices: their instability at the nanoscale, their insulating character and the lack of control when positioning nanocrystals in nanodevices. Here we show the encapsulation of robust Fe-based SCO molecules within the 1D cavities of single-walled carbon nanotubes (SWCNT). We find that the SCO mechanism endures encapsulation and positioning of individual heterostructures in nanoscale transistors. The SCO switch in the guest molecules triggers a large conductance bistability through the host SWCNT. Moreover, the SCO transition shifts to higher temperatures and displays hysteresis cycles, and thus memory effect, not present in crystalline samples. Our results demonstrate how encapsulation in SWCNTs provides the backbone for the readout and positioning of SCO molecules into nanodevices, and can also help to tune their magnetic properties at the nanoscale.

Theoretical inspection of the spin-crossover [Fe(tzpy)2(NCS)2] complex on Au(100) surface.

We explore the deposition of the spin-crossover [Fe(tzpy)2(NCS)2] complex on the Au(100) surface by means of density functional theory (DFT) based calculations. Two different routes have been employed: low-cost finite cluster-based calculations, where both the Fe complex and the surface are maintained fixed while the molecule approaches the surface; and periodic DFT plane-wave calculations, where the surface is represented by a four-layer slab and both the molecule and surface are relaxed. Our results show that the bridge adsorption site is preferred over the on-top and fourfold hollow ones for both spin states, although they are energetically close. The LS molecule is stabilized by the surface, and the HS-LS energy difference is enhanced by about 15%-25% once deposited. The different Fe ligand field for LS and HS molecules manifests on the composition and energy of the low-lying bands. Our simulated STM images indicate that it is possible to distinguish the spin state of the deposited molecules by tuning the bias voltage of the STM tip. Finally, it should be noted that the use of a reduced size cluster to simulate the Au(100) surface proves to be a low-cost and reliable strategy, providing results in good agreement with those resulting from state-of-the-art periodic calculations for this system.

Deposition of the Spin Crossover FeII -Pyrazolylborate Complex on Au(111) Surface at the Molecular Level.

The interaction at the molecular level of the spin-crossover (SCO) FeII ((3,5-(CH3 )2 Pz)3 BH)2 complex with the Au(111) surface is analyzed by means of rPBE periodic calculations. Our results show that the adsorption on the metallic surface enhances the transition energy, increasing the relative stability of the low spin (LS) state. The interaction indeed is spin-dependent, stronger for the low spin than the high spin (HS) state. The different strength of the Fe ligand field at low and high temperature manifests on the nature, spatial extension and relative energy of the states close to the Fermi level, with a larger metal-ligand hybridization in the LS state. This feature is of relevance for the differential adsorption of the LS and HS molecules, the spin-dependent conductance, and for the differences found in the corresponding STM images, correctly reproduced from the density of states provided by the rPBE calculations. It is expected that this spin dependence will be a general feature of the SCO molecule-substrate interaction, since it is rooted in the different ligand field of Fe site at low and high temperatures, a common hallmark of the FeII SCO complexes. Finally, the states involved in the LIESST phenomenon has been identified through NEVPT2 calculations on a model reaction path. A tentative pathway for the photoinduced LS→HS transition is proposed, that does not involve the intermediate triplet states, and nicely reproduces both the blue laser wavelength required for the activation, and the wavelength of the reverse HS → LS transition.

Transient Sub-nanosecond Soft X-ray NEXAFS Spectroscopy on Organic Thin Films.

We demonstrate visible pump soft X-ray probe near-edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements at the carbon K edge on thin molecular films in the laboratory. This opens new opportunities through the use of laboratory equipment for chemical speciation. We investigate the metal-free porphyrin derivative tetra(tert-butyl)porphyrazine as an ideal model system to elucidate electronic properties of tetrapyrroles like chlorophyll or heme. In contrast to measurements in gas or liquid state, the investigation of thin films is of high interest in the field of optoelectronic and photovoltaic devices though challenging due to the low damage thresholds of the samples upon excitation. With a careful pre-characterization using optical techniques, successful measurements were performed using a NEXAFS spectrometer based on a laser-produced plasma source and reflection zone plates with a resolving power of 1000 and a time resolution of 0.5 ns. In combination with density functional theory calculations, first insights into a long-lived excitonic state are gained and discussed.

Theoretical study of the photoconduction and photomagnetism of the BPY[Ni(dmit)2]2 molecular crystal.

The BPY[Ni(dmit)2]2 molecular crystal synthesized by Naito and coworkers (J. Am. Chem. Soc., 2012, 134, 18656) was characterized as a photo-magnetic-conductor. This crystal is a nonmagnetic semiconductor in the dark and becomes a magnetic conductor after UV irradiation. This work analyzes the key ingredients of the observed photomagnetism and photoconduction by means of wavefunction-based calculations on selected fragments and periodic calculations on the whole crystal. Our results demonstrate that UV-Vis light induces charge transfer processes between the closest [Ni(dmit)2]- and BPY2+ units, that introduce unpaired electrons on the unoccupied orbitals of the BPY cations. Since the conduction bands present a strong mixing of BPY and Ni(dmit)2, the optically activated anion-cation charge transfer enhances the conductivity. The photoinduced (BPY2+)* radicals can indeed interact with the close Ni(dmit)2 units, with non-negligible spin-spin magnetic couplings, which are responsible for the changes induced by the irradiation on the temperature dependence of the magnetic susceptibility.

Light-Induced Spin Transitions in Copper-Nitroxide-Based Switchable Molecular Magnets: Insights from Periodic DFT+U Calculations.

The electronic structure and magnetic interactions of three members of the breathing crystal Cu(hfac)2 LR family (hfac=hexafluoroacetylacetonato, LR =pyrazole-substituted nitronyl nitroxides with R=Me, Et, Pr, iPr, Bu ), mainly Cu(hfac)2 LPr (1), Cu(hfac)2 LBu ⋅0.5 C8 H18 (2) and Cu(hfac)2 LBu ⋅0.5 C8 H10 (3), have been analyzed by means of periodic plane-wave based DFT+U calculations. These CuII -nitroxide based molecular magnets display thermally and optically induced switchable behavior and light-induced excited spin state trapping phenomena. The calculations confirm the presence of temperature-dependent exchange interaction within the spin triads formed by the nitroxide-copper(II)-nitroxide units, in line with the changes observed in the effective magnetic moment. Moreover, they quantify the interchain interaction mediated by the terminal nitroxide group of two spin triads in neighboring polymer chains. This interaction competes with the exchange interaction within the spin triads at high temperature, and introduces 1D exchange channels that do not coincide with the polymeric chains. The density of states reveal that the low-lying conduction states potentially involved in the UV/Vis transitions are located on the nitroxide radicals, the hfac groups and the Cu atoms. Then, the density of states is almost independent of the solvent and the R group. This suggests the possibility of light-induced spin switching for other members of this family. The 500 nm band of the low-temperature phase can be ascribed to a ligand-to-metal charge transfer transition between the nitroxide and Cu bands.

On the Electronic Structure of Cu Chlorophyllin and Its Breakdown Products: A Carbon K-Edge X-ray Absorption Spectroscopy Study.

Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, the carbon backbone of sodium copper chlorophyllin (SCC), a widely used chlorophyll derivative, and its breakdown products are analyzed to elucidate their electronic structure and physicochemical properties. Using various sample preparation methods and complementary spectroscopic methods (including UV/Vis, X-ray photoelectron spectroscopy), a comprehensive insight into the SCC breakdown process is presented. The experimental results are supported by density functional theory calculations, allowing a detailed assignment of characteristic NEXAFS features to specific C bonds. SCC can be seen as a model system for the large group of porphyrins; thus, this work provides a novel and detailed description of the electronic structure of the carbon backbone of those molecules and their breakdown products. The achieved results also promise prospective optical pump/X-ray probe investigations of dynamic processes in chlorophyll-containing photosynthetic complexes to be analyzed more precisely.

Evaluation of the Giant Ferromagnetic π-d Interaction in Iron-Phthalocyanine Molecule.

The interaction between itinerant π and localized d electrons in metal-phthalocyanines, namely, Jπd interaction, is considered as responsible for the giant negative magnetoresistance observed in several phthalocyanine-based conductors, among many other important physical properties. Despite the fundamental and technological importance of this on-site intramolecular interaction, its giant ferromagnetic nature has been only recently demonstrated by the experiments conducted by Murakawa et al. in the neutral radical [Fe(Pc)(CN)2]·2CHCl3 ( Phys. Rev. B 2015 , 92 , 054429 ). In this article, we present the theoretical evaluation of this interaction combining wave function-based electronic calculations on isolated Fe(Pc)(CN)2 molecules and density functional theory-based periodic calculations on the crystal. Our calculations confirm the ferromagnetic nature of the π-d interaction, with a coupling constant as large as Jπd/kB = 570 K, in excellent agreement with the experiments, and the presence of intermolecular antiferromagnetic interactions driven by the π-π overlap of neighboring phthalocyaninato molecules. The analysis of the wave function of the ground state of the Fe(Pc)(CN)2 molecule provides the clues of the origin of this giant ferromagnetic π-d interaction.

On the nature of hydrogen bonds to platinum(II)--which interaction can predict their strength?

The interaction between hydrogen bond donors and platinum has been analysed. Our results point to an interaction that can be entirely predicted from the dz(2) orbital energy of the platinum centre indicating strong charge transfer, with significant dispersion contribution to the bonding, very different from classical hydrogen bonds.

One site is enough: a theoretical investigation of iron-catalyzed dehydrogenation of formic Acid.

Dehydrogenation of HCO2H: The reaction mechanism for the dehydrogenation of formic acid catalyzed by a highly active and selective iron complex has been studied by DFT. The most favorable pathway shows the hydride in Fe-H complexes acting as a spectator ligand throughout the catalytic cycle. This result opens up the Fe complex for modification in order to achieve more efficient and selective catalysts.

Molecular modification of coumarin dyes for more efficient dye sensitized solar cells.

In this work, new coumarin based dyes for dye sensitized solar cells (DSSC) have been designed by introducing several substituent groups in different positions of the NKX-2311 structure. Two types of substitutions have been considered: the introduction of three electron-donating groups (-OH, -NH(2), and -OCH(3)) and two different substituents with steric effect: -CH(2)-CH(2)-CH(2)- and -CH(2)-HC=CH-. The electronic absorption spectra (position and width of the first band and absorption threshold) and the position of the LUMO level related to the conduction band have been used as theoretical criteria to evaluate the efficiency of the new dyes. The introduction of a -NH(2) group produces a redshift of the absorption maximum position and the absorption threshold, which could improve the cell efficiency. In contrast, the introduction of -CH(2)-CH(2)-CH(2)- does not modify significantly the electronic structure of NKX-2311, but it might prevent aggregation. Finally, -CH(2)-HC=CH- produces important changes both in the electronic spectrum and in the electronic structure of the dye, and it would be expected as an improvement of cell efficiency for these dyes.

Coumarin derivatives for dye sensitized solar cells: a TD-DFT study.

Time dependent density functional theory (TD-DFT) calculations have been carried out to study the electronic structure and the optical properties of five coumarin based dyes: C343, NKX-2311, NKX-2586, NKX-2753 and NKX-2593. We have found out that the position and width of the first band in the electronic absorption spectra, the absorption threshold and the LUMO energy with respect to the conduction band edge are key parameters in order to establish some criteria that allow evaluating the efficiency of coumarin derivatives as sensitizers in Dye Sensitized Solar Cells (DSSC). Those criteria predict the efficiency ordering for the coumarin series in good agreement with the experimental evidence. Presumably, they might be used in the design of new efficient organic based DSSC.

Real-Time TD-DFT Simulations in Dye Sensitized Solar Cells: The Electronic Absorption Spectrum of Alizarin Supported on TiO2 Nanoclusters.

The structural and electronic properties of the alizarin dye supported on TiO2 nanoclusters have been examined by means of time-dependent density-functional (TD-DFT) calculations performed in the time-domain framework. The calculated electronic absorption spectrum of free alizarin shows a first band centered at 2.67 eV that upon adsorption features a red shift by 0.31 eV, in agreement with both experimental and previous theoretical work. This red shift arises from a relative stabilization of the dye LUMO when adsorbed. To analyze the dependence of the electronic properties of the dye-support couple on the size of metal-oxide nanoparticles, different models of (TiO2)n nanoclusters have been used (with n = 1, 2, 3, 6, 9, 15, and 38). As a conclusion, the minimal model is good enough to theoretically reproduce the main feature in the spectrum (i.e., the energy shift of the main band upon binding to TiO2). However, it fails in creating intermediate states which could play a significant role under real experimental conditions (dynamics of the electronic transfer). Indeed, as the size of the nanocluster grows, the dye LUMO moves from the edge to well inside the conduction band (Ti 3d band). On the other hand, to assess the consistency of the time-domain approach in the case of such systems, conventional (frequency-domain) TD-DFT calculations have been carried out. It is found that, as far as the functional and basis set are equivalent, both approaches lead to similar results. While for small systems the standard TD-DFT is better suited, for medium to large sized systems, the real-time TD-DFT becomes competitive and more efficient.