Selective Transition Enhancement in a g-Engineered Diradical.

A diradical with engineered g-asymmetry was synthesized by grafting a nitroxide radical onto the [Y(Pc)2]⋅ radical platform. Various spectroscopic techniques and computational studies revealed that the electronic structures of the two spin systems remained minimally affected within the diradical system. Fluid-solution Electron Paramagnetic Resonance (EPR) experiments revealed a weak exchange coupling with |J| ~ 0.014 cm-1, subsequently rationalized by CAS-SCF calculations. Frozen solution continuous-wave (CW) EPR experiments showed a complicated and power-dependent spectrum that eluded analysis using the point-dipole model. Pulse EPR manipulations with varying microwave powers, or under varying magnetic fields, demonstrated that different resonances could be selectively enhanced or suppressed, based on their different tipping angles. In particular, Field-Swept Echo-Detected (FSED) spectra revealed absorptions of MW power-dependent intensities, while Field-Swept Spin Nutation (FSSN) experiments revealed two distinct Rabi frequencies. This study introduces a methodology to synthesize and characterize g-asymmetric two-spin systems, of interest in the implementation of spin-based CNOT gates.

Voltage-induced modulation of the magnetic exchange in binuclear Fe(III) complex deposited on Au(111) surface.

We present a complete computational study devoted to the deposition of a magnetic binuclear complex on a metallic surface, aimed to obtain insight into the interaction of magnetically coupled complexes with their supporting substrates, as well as their response to external electrical stimuli applied through a surface-molecule-STM molecular junction-like architecture. Our results not only show that the deposition is favorable in two of the four studied orientations, but also, that the magnetic coupling is only slightly perturbed once the complex is adsorbed. We observe that the effects of the applied bias voltage on the magnetic coupling strongly depend on the molecule orientation with respect to the surface and the voltage polarity. Further analysis shows that this behavior is attributable to the stabilization/destabilization of the d-type singly occupied orbitals of the iron centers, reinforced by the strong local electric fields and induced charge densities only present in certain orientations of the deposited molecule and applied voltage polarity.

Near-infrared absorption of fused core-modified expanded porphyrins for dye-sensitized solar cells.

Photophysical, photovoltaic, and charge transport properties of fused core-modified expanded porphyrins containing two pyrroles, one dithienothiophene (DTT) unit, and 1-4 thiophenes (1-4) were inspected by using density functional theory (DFT) and time-dependent DFT. Compounds 1-3 have been investigated experimentally before, but 4 is a theoretical proposal whose photophysical features match those extrapolated from 1 to 3. They exhibit absorption in the range of 700-970 nm for their Q bands and 500-645 nm for their Soret bands. The rise of thiophene rings placed in front of the DTT unit in the expanded porphyrin ring causes a bathochromic shift of the longest absorption wavelength, leading to near-infrared absorptions, which represent 49% of the solar energy. All the systems show a thermodynamically favorable process for the electron injection from the dye to TiO2 and adsorption on a finite TiO2 model. The electron regeneration of the dye is only thermodynamically feasible for the smallest expanded porphyrins 1 and 2 when I-/I3- electrolyte is used. The charge transport study shows that for voltages lower than 0.4 V, junctions featuring pentaphyrin 1 and octaphyrin 4 are more conductive than those containing hexaphyrin 2 or heptaphyrin 3. The results showed that the four fused core-modified expanded porphyrins investigated are potential dyes for applications in dye-sensitized solar cells, mainly pentaphyrin 1 and hexaphyrin 2. Moreover, increasing the number of thiophene rings in the macrocycle proved fruitful in favoring absorption in the near-infrared region, which is highly desired for dye-sensitized solar cells.

Computational demonstration of isomer- and spin-state-dependent charge transport in molecular junctions composed of charge-neutral iron(II) spin-crossover complexes.

Chemistry offers a multitude of opportunities towards harnessing functional molecular materials with application propensity. One emerging area of interest is molecular spintronics, in which charge and spin degrees of freedom have been used to achieve power-efficient device architectures. Herein, we show that, with the aid of state-of-the-art quantum chemical calculations on designer molecular junctions, the conductance and spin filtering capabilities are molecular structure-dependent. As inferred from the calculations, structural control over the transport can be achieved by changing the position of the thiomethyl (SMe) anchoring groups for Au(111) electrodes in a set of isomeric 2,2'-bipyridine-based metal coordinating ligand entities L1 and L2. The computational studies on heteroleptic iron(II) coordination complexes (1 and 2) composed of L1 and L2 reveal that switching the spin-state of the iron(II) centers, from the low-spin (LS) to high-spin (HS) state, by means of an external electric field stimulus, could, in theory, be performed. Such switching, known as spin-crossover (SCO), renders charge transport through single-molecule junctions of 1 and 2 spin-state-dependent, and the HS junctions are more conductive than the LS junctions for both complexes. Additionally, the LS and HS junctions based on complex 1 are more conductive than those featuring complex 2. Moreover, it is predicted that the spin filtering efficiency (SFE) of the HS junctions strongly depends on the bridging complex geometry, with 1 showing a voltage-dependent SFE, whereas 2 exhibits an SFE of practically 100% over all the studied voltage range. To be pragmatic towards applications, the ligands L1 and L2 and complex 1 have been successfully synthesized, and the spin-state switching propensity of 1 in the bulk state has been elucidated. The results shown in this study might lead to the synthesis and characterization of isomeric SCO complexes with tuneable spin-state switching and charge transport properties.

Fullerene binding effects in Al(III)/Zn(II) Porphyrin/Phthalocyanine photophysical properties and charge transport.

We evaluate the fullerene C60 binding effect; through the metal (Al) and through the ligand (Pc,TPP), on the photophysical and charge transport properties of M-porphyrin(TPP)/phthalocyanine(Pc) (M = Al(III), Zn(II)). We perform density functional theory (DFT) and time-dependent DFT calculations for the macrocycle-C60 dyads, showing that all systems studied are thermodynamically favorable. The C60 binding effect on the absorption spectrum is a red-shift of the Q and Soret (B) bands of TPPs and Pcs. The Pc-dyads show longer λ for Q bands (673 nm) than those with TPP (568 nm). AlTPP-C60 and ZnTPP-C60 show a more favorable electron injection to TiO2 than the analogs Pcs, and the regeneration of the dye is preferred in AlTPP-C60 and AlPc-C60. Zero-bias conductance is computed (10-4-10-7 G0) for the dyads using molecular junctions with Au(111)-based electrodes. When a bias voltage of around 0.6 V up to 1 V is applied, an increase in current is obtained for AlTPP-C60 (10-7 A), ZnTPP-C60 (10-7 A), and AlPc-C60 (10-8 A). Although there is not a unique trend in the behavior of the dyads, Pcs have better photophysical properties than TPPs and the latter are better in the charge transport. We conclude that AlTPP(ZnTPP)-C60 dyads are an excellent alternative for designing new materials for dye-sensitized solar cells or optoelectronic devices.

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.

Assessment of New Expanded Porpholactones as UV/Vis/NIR Chromophores for Dye-Sensitized Solar Cell Applications.

Expanded porphyrins arise as an alternative for potential application as chromophores in dye-sensitized solar cells. (DSSCs). The modification of the core of these compounds provides remarkable changes in the photoelectronic behavior. In the present article, the improvement of its properties for a potential application as UV/vis/NIR chromophores in DSSCs has been studied, when an oxazolone moiety has replaced an imine ring in analogy to the porpholactones first synthesized by Crossley et al. ( J. Chem. Soc., Chem. Commun. 1984, 920-922). These expanded porpholactones present a noticeable red shift as well as an increase in the intensity of the Q-bands regarding the parent compounds. The photophysical properties of Sapphyrin have been explored through DFT calculations and vibrationally resolved absorption spectra simulations. Energetic parameters showed favorable electron injection from the chromophore to the TiO2 semiconductor. In addition, aromaticity was analyzed and rationalized using magnetic and delocalization criteria. Results showed qualitatively similar trends between aromaticity descriptors and Q bands giving a great opportunity to the use this property in the rational design of chromophores. Finally, the nonequilibrium Green's function formalism shows the ability of expanded porpholactones in electron transport.

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.

Spin-filter transport and magnetic properties in a binuclear Cu(ii) expanded porphyrin based molecular junction.

Although the magnetic and transport properties of molecular junction systems composed of metalled porphyrins or phthalocyanines have been broadly studied in recent years, to date no studies have been devoted to evaluate the aforementioned properties in junction systems featuring metalled expanded porphyrins as active elements. The present work reports a detailed theoretical study of the magnetic and electronic transport properties of the recently synthesized dinuclear Cu(ii)-naphthoisoamethyrin complex (PyCu2). This is the first work on performing these kinds of studies using a magnetically coupled metallic expanded porphyrin as a molecular kernel. DFT and wave function-based methods have been used to determine the nature of the magnetic interaction between the metallic centres, characterized by the exchange coupling constant J, showing that although this was found to be weakly antiferromagnetic, after an exhaustive analysis it turns out that the coupling has a ferromagnetic nature with a value of J = 14.2 cm-1. Once the magnetic ground state of PyCu2 was rigorously established, the spin resolved transport properties of the device composed of the expanded porphyrin attached to two gold nano-wires were studied by means of the combination of DFT and the nonequilibrium Green's function formalism, in order to explore PyCu2 prospects as a possible spintronic device.