A Norbornadiene-Based Molecular System for the Storage of Solar-Thermal Energy in an Aqueous Solution: Study of the Heat-Release Process Triggered by a Co(II)-Complex.

It is urgent yet challenging to develop new environmentally friendly and cost-effective sources of energy. Molecular solar thermal (MOST) systems for energy capture and storage are a promising option. With this in mind, we have prepared a new water-soluble (pH > 6) norbornadiene derivative (HNBD1) whose MOST properties are reported here. HNBD1 shows a better matching to the solar spectrum compared to unmodified norbornadiene, with an onset absorbance of λonset = 364 nm. The corresponding quadricyclane photoisomer (HQC1) is quantitatively generated through the light irradiation of HNBD1. In an alkaline aqueous solution, the MOST system consists of the NBD1-/QC1- pair of deprotonated species. QC1- is very stable toward thermal back-conversion to NBD1-; it is absolutely stable at 298 K for three months and shows a marked resistance to temperature increase (half-life t½ = 587 h at 371 K). Yet, it rapidly (t½ = 11 min) releases the stored energy in the presence of the Co(II) porphyrin catalyst Co-TPPC (ΔHstorage = 65(2) kJ∙mol-1). Under the explored conditions, Co-TPPC maintains its catalytic activity for at least 200 turnovers. These results are very promising for the creation of MOST systems that work in water, a very interesting solvent for environmental sustainability, and offer a strong incentive to continue research towards this goal.

Multi-target heteroleptic palladium bisphosphonate complexes.

Bisphosphonates are the most commonly prescribed drugs for the treatment of osteoporosis and other bone illnesses. Some of them have also shown antiparasitic activity. In search of improving the pharmacological profile of commercial bisphosphonates, our group had previously developed first row transition metal complexes with N-containing bisphosphonates (NBPs). In this work, we extended our studies to heteroleptic palladium-NBP complexes including DNA intercalating polypyridyl co-ligands (NN) with the aim of obtaining potential multi-target species. Complexes of the formula [Pd(NBP)2(NN)]·2NaCl·xH2O with NBP = alendronate (ale) or pamidronate (pam) and NN = 1,10 phenanthroline (phen) or 2,2'-bipyridine (bpy) were synthesized and fully characterized. All the obtained compounds were much more active in vitro against T. cruzi (amastigote form) than the corresponding NBP ligands. In addition, complexes were nontoxic to mammalian cells up to 50-100 µM. Compounds with phen as ligand were 15 times more active than their bpy analogous. Related to the potential mechanism of action, all complexes were potent inhibitors of two parasitic enzymes of the isoprenoid biosynthetic pathway. No correlation between the anti-T. cruzi activity and the enzymatic inhibition results was observed. On the contrary, the high antiparasitic activity of phen-containing complexes could be related to their ability to interact with DNA in an intercalative-like mode. These rationally designed compounds are good candidates for further studies and good leaders for future drug developments. Four new palladium heteroleptic complexes with N-containing commercial bisphosphonates and DNA intercalating polypyridyl co-ligands were synthesized and fully characterized. All complexes displayed high anti-T. cruzi activity which could be related to the inhibition of the parasitic farnesyl diphosphate synthase enzyme but mainly to their ability to interact DNA.

New complexes of Cu(II) with dipicolinate and pyridyl-based ligands: An experimental and DFT approach.

The three novel mononuclear copper(II) complexes with dipicolinate and pyridyl-based ligands [Cu(dipic)(L)(OH2)] (L=4-picoline, vinylpyridine, 4-styrylpyridine; dipic2-=dipicolinate) were afforded and structurally characterized. X-ray diffraction studies accounted for slight distorted square-pyramidal structures in which the dianion dipic2- acts as a tridentate ligand in a mer-fashion, the N-donor species occupy an in-plane position, and a water molecule was detected apically coordinated. To assess the effect of the nature of the pyridyl-substituent (para position) on electronic properties, other complexes were also synthesized: [Cu(dipic)(py)(OH2)], [{Cu(dipic)(OH2)}2(µ-pyz)] and [{Cu(dipic)(OH2)}(µ-pypy){Cu(dipic)}] (py=pyridine, pyz=pyrazine, pypy=(E)-1,2-bis(pyridine-4-yl)ethane). Absorptive behavior in the UV-VIS region was studied in solution and in the solid state (reflectance measurements). Additionally, geometry and population analyses were conducted by means of DFT calculations. Electronic UV-VIS spectra were simulated for both dinuclear complexes in the framework of the TD-DFT methodology to assign the origin of the absorption bands.

Nickel(II) complexes with methyl(2-pyridyl)ketone oxime: synthesis, crystal structures and DFT calculations.

The synthesis and structural characterization of the three novel nickel(II) complexes [Ni(OOCPh)(2)(mpkoH)(2)] (1), [Ni(NO(3))(2)(mpkoH)(2)] (2) and [Ni(mpkoH)(3)](NO(3))(2)·½H(2)O (3·½H(2)O), with mpkoH=methyl(2-pyridyl)ketone oxime is reported. Geometry optimization and population analyses were performed by means of DFT calculations for the previously mentioned compounds as well as for [NiCl(2)(mpkoH)(2)] (4). Electronic UV-vis spectra were also simulated in the TD-DFT framework to assign the origin of the absorption bands and in doing so, to have a clear picture of the absorptive features of the coordination compounds under investigation.

Dinuclear triple-stranded complexes of Re(V) with bis(benzene-o-dithiolato) ligands.

The reaction of K(2)ReCl(6) with 1,2-bis(2,3-dimercaptobenzamido)ethane (H(4)-1), and 1,2-bis(2,3-dimercaptobenzamido)benzene (H(4)-2) in the presence of Na(2)CO(3) in methanol affords dinuclear complexes of Re(V). Experimental evidence supports the presence of self-assembled complexes with two {Re(S(2)C(6)H(3))(3)} units connected in a triple-stranded fashion. Density Functional Theory (DFT) studies on geometry and electronic properties were conducted employing the hybrid B3LYP and PBE1PBE functionals. The helical (ΔΔ and ΛΛ) and meso-helical (ΔΛ) isomers were considered. For the helicate complexes included in this study, differences in the stability of the isomers were observed originating in different steric and strain interactions between the three ligand strands. The geometries at the minimum exhibit a distorted trigonal-prismatic coordination environment at the metal centers. Natural bond orbitals (NBO) analysis indicates the presence of Re-S bonds which are strongly polarized toward the non-metal. Time-Dependent DFT (TD-DFT) calculations were performed for a further understanding of the optical spectra. The calculations show the occupied 5d orbitals of the rhenium lying beneath occupied sulfur-based MOs. The general features of the electronic spectra in the visible region are reasonably reproduced by the calculations. The analysis of molecular orbitals also allows the assignment of the origin for all experimentally detected absorption bands. In the high-energy region of the spectrum the absorptions are attributed to ligand-to-metal-ligand charge transfer (LMLCT), in which sulfur-based orbitals and unoccupied orbitals at the rhenium atom and the benzene-o-dithiolato groups are involved. Also in the blue region, shoulders originating from LMLCT are observed.

Solution phase photolysis of 1,2-dithiane alone and with single-walled carbon nanotubes.

Photolysis of 1,2-dithiane (1) in acetonitrile with single walled carbon nanotubes (SWCNTs) was earlier reported to form thiol-functionalized SWCNTs via the butane-1,4-dithiyl diradical (2). The present study shows that 2 instead undergoes a facile rearrangement to thiophane-2-thiol (6). This photoreaction is clean, rapid, and irreversible under 313 nm irradiation. The secondary photolysis of 6 with SWCNTs at a shorter wavelength (254 nm) leads to 2-thiophanyl radicals 8, which derivatize SWCNTs by covalent attachment. Pyrolysis of the resulting "sulfurized SWCNTs" affords a mixture of organosulfur compounds, including thiophene formed by dehydrogenation. An unknown additional mechanism causes high TGA weight loss and a large incorporation of sulfur.

TD-DFT investigation of triple-stranded helicates with bis(benzene-o-dithiolato) ligands.

The electronic spectra of triple-stranded complexes of Ti(IV) with bis(benzene-o-dithiolato) ligands (H(4)-L(1)=1,2-bis(2,3-dimercaptobenzamido)ethane; H(4)-L(2)=1,2-bis(2,3-dimercaptobenzamido)benzene) were investigated at the TD-DFT level of theory employing B3LYP/LANL2DZ. The influence of the nature (aliphatic or aromatic) of the spacer bridging both {Ti(S(2)C(6)H(3))(3)} units on the absorptive features of the dinuclear complexes was also studied. B3LYP/LANL2DZ leads to spectra accounting for four absorption bands. At the lowest-energy region, the most important transitions are due to ligand-to-metal charge transfer (LMCT), in which out-of-plane ligand-centered orbitals and titanium-based MOs are involved. In going to the blue-region, a third band was detected with excitations showing an important contribution from ligand-to-ligand charge transfer (LLCT) and indeed, a combined LMCT+LLCT character has been considered. This observation seems to arise from a decrease in the metallic character of the LUMO-derivatives involved in the excitations. The origin of the absorption band at the highest-energy part of the spectrum is assigned to a LLCT. The influence of the nature of the spacer on the molar absorption coefficients (ɛ) for this band has been clearly observed. The complex bearing aliphatic spacer shows ɛ of about 5 E+4 M(-1) cm(-1), while the one containing an aromatic spacer present a value of ɛ of about 2 E+5 M(-1) cm(-1).

Time-dependent density functional theory investigation of the electronic spectra of hexanuclear chalcohalide rhenium(III) clusters.

The UV-vis spectra of the hexanuclear chalcohalide rhenium(III) clusters of formula [Re(6)S(8)X(6)](4-) (X(-) = Cl(-), Br(-), I(-)) were investigated at the time-dependent density functional theory (TD-DFT) level employing B3LYP, PBE1PBE, and the double-hybrid B2PLYP functional in combination with the LANL2DZ basis set. We were able to reproduce the red shift experimentally observed when the halide changes from chloride to iodide. However, some discrepancies between experimental results and theory were found. First, we did not observe a remarkable dependence of the experimental ill-resolved bands on the solvent. Indeed, similar spectra were obtained taken CH(2)Cl(2) or CH(3)CN as solvents into account. Second, all calculations explained the origin of the band peaked at the low-energy region in contraposition with the one experimentally assumed by R. Long et al. (J. Am. Chem. Soc. 1996, 118, 4603), and theoretically made available by Arratia-Pérez et al. (J. Chem. Phys. 1999, 110, 2529). These authors have proposed a ligand-to-cluster charge transfer (LCCT) for all title complexes. Our findings undoubtedly allow such origin to be discarded. While the HGGA functionals lead to a cluster-to-halide ligand charge transfer (CLCT), an intracluster charge transfer (ICCT) has been considered by employing B2PLYP. This contribution showed B2PLYP in the presence of the solvent to be the best performer in studying the UV-vis spectra of large complexes of rhenium(III) containing the Re-S bond. We strongly recommended the use of the double-hybrid B2PLYP in studying UV-vis spectrum of rhenium complexes of size making the computational cost affordable. We expect that our work stimulates new experimental and theoretical investigations of the title complexes to confirm our assignment.

Electronic spectra of oxocomplexes of Re(V) with thiolato ligands.

The electronic spectra of monooxo complexes of rhenium(V) with 1,2-benzenedithiolato (bdt(2-)), 3,4-toluenenedithiolato (tdt(2-)), maleonitriledithiolato (mnt(2-)), and 1,2-dithiooxalato (dto(2-)) ligands were investigated at the TD-DFT level employing several functionals and basis sets. The most important transitions are due to ligand-to-metal charge transfer (LMCT) with some minor contribution of ligand-to-metal-ligand charge transfer (LMLCT). However, for [ReO(dto)(2)](-) this statement does not hold because the transitions are due to metal-ligand-to-metal-ligand charge transfer (MLMLCT). This observation arises from the presence of the oxalate groups. These substituents increase the flexibility of this complex with respect to the complexes containing bdt(2-), mnt(2-) and tdt(2-). In these complexes, the C-C backbone imposes a rigid geometry, which leads to the occupied rhenium-orbitals lying energetically below the sulfur-based orbitals. For the complexes [ReO(bdt)(2)](-), [ReO(mnt)(2)](-) and [ReO(tdt)(2)](-), the HOMO is a sulfur-based out-of-plane molecular orbital. However, the HOMO of [ReO(dto)(2)](-) shows a high contribution of the rhenium d(x)(2)(-y)(2) and in-plane sulfur-centered orbitals. The comparison of the results obtained with several functionals clearly point to the PBE1PBE/LANL2DZ method as the best TD-DFT method to investigate the electronic spectra of monooxo complexes of Re(V) with thiolato ligands. The results obtained with larger basis sets suggest that the agreement between experiment and theory was due to an error cancellation between basis set incompleteness and deficiencies in the DFT methods.

Thermodynamic study of proton transfer reactions of Re(V) trans-dioxocomplexes in aqueous solution.

The thermodynamics of protonation of trans-[Re(V)O(2)L(2)](+) (L = aliphatic di and polyamines) complexes in aqueous solution was studied by using experimental and theoretical approaches. The complexes containing diamines undergo protonation on the oxo ligands, whereas those containing polydentate amines protonate on uncoordinated amino groups. The protonation reactions were studied experimentally by microcalorimetric techniques, in all cases exothermic with |DeltaH degrees | ranging from 7 to 50 kJ/mol. For complexes containing diamines, the exothermicity was in concordance with the basicities in some cases, while in others no systematic behaviour was found. For complexes with polydentate amines, the enthalpy dominates with a modest influence on the entropy. Theoretically, Density Functional Theory (DFT) methods were employed in the gas phase, and bulk solvent effects were treated by means of the Polarizable Continuum Model. Direct solute-solvent effects were considered adding explicit water molecules. The enthalpy change calculated in the gas phase was in marked disagreement with the experimental results due to the relevancy of solvation/desolvation processes. The explicit inclusion of water molecules led to a good improvement. A discrete-continuum model was also employed, for which DeltaG degrees was overestimated in all cases. Further investigations, both experimental and theoretical are necessary to get a more complete picture of the proton transfer reactions of these complexes. The experimental values herein determined constitute the first step to construct a set of data to which it is possible to benchmark new theoretical approaches to compute the thermodynamics of proton transfer reactions of metal complexes in aqueous solution.

Myoglobin modified electrodes as anchors for d metal cationic complexes.

The capability of adsorption of different electroactive cationic Re(V)-amine complexes onto myoglobin-containing electrodes has been investigated. The goal of this work was the development of an Au/thiol/myo electrode and, after incubation of such ensemble in the presence of three different Re(V)-amine complexes, the evaluation of the extent of surface coverage by the complexes (as a way to evaluate the interaction complex-protein) using electrochemical techniques. Our results showed that a protein-containing electrode could therefore be used for the detection of the interaction of small electroactive cationic complexes and the biomolecule. The extent of the coverage of the myoglobin electrode by the complex depends on the number of free tails from the ligands and the total charge of the complex.

Voltammetric studies of the interaction between Re(V) complexes and proteins.

A reliable method based on electrochemical measurements for the evaluation of protein interaction with small electroactive coordination compounds is proposed. Protein binding capacity of five different cationic Re(V) complexes was evaluated by means of voltammetric techniques in the absence and the presence of bovine serum albumin. The percentage of interaction between the complex and the protein was estimated from the quantitative decrease of the diffusion coefficient for the sole complex due to the addition of the protein, and therefore the formation of the protein-complex molecular ensemble. The proposed methodology was checked using cisplatin as a molecular complex probe.