Syntheses and structure of dinuclear metal complexes containing naphthyl-Ir bichromophore

A series of novel metal complexes were synthesized containing an Ir-cyclometalated bichromophore as a visible-light sensitizer.

When Molecular Magnetism Meets Supramolecular Chemistry: Multifunctional and Multiresponsive Dicopper(II) Metallacyclophanes as Proof-of-Concept for Single-Molecule Spintronics and Quantum Computing Technologies?

Molecular magnetism has made a long journey, from the fundamental studies on through-ligand electron exchange magnetic interactions in dinuclear metal complexes with extended organic bridges to the more recent exploration of their electron spin transport and quantum coherence properties. Such a field has witnessed a renaissance of dinuclear metallacyclic systems as new experimental and theoretical models for single-molecule spintronics and quantum computing, due to the intercrossing between molecular magnetism and metallosupramolecular chemistry. The present review reports a state-of-the-art overview as well as future perspectives on the use of oxamato-based dicopper(II) metallacyclophanes as promising candidates to make multifunctional and multiresponsive, single-molecule magnetic (nano)devices for the physical implementation of quantum information processing (QIP). They incorporate molecular magnetic couplers, transformers, and wires, controlling and facilitating the spin communication, as well as molecular magnetic rectifiers, transistors, and switches, exhibiting a bistable (ON/OFF) spin behavior under external stimuli (chemical, electronic, or photonic). Special focus is placed on the extensive research work done by Professor Francesc Lloret, an outstanding chemist, excellent teacher, best friend, and colleague, in recognition of his invaluable contributions to molecular magnetism on the occasion of his 65th birthday.

Dinuclear metal complexes: multifunctional properties and applications

Dinuclear metal complexes have enabled breakthroughs in OLEDs, photocatalytic water splitting and CO2 reduction, DSPEC, chemosensors, biosensors, PDT and smart materials.

Guest encapsulations in non-porous crystals of fully fluorinated dinuclear metal complexes with the M2O2 core (M = Fe3+, Co2+, Ni2+)

Two different coordination types of fully fluorinated dinuclear metal complexes, [Fe2L4(OMe)2] and [M2L4(OH2)2] (M = Co2+, Ni2+), form non-porous crystals, which act as hosts for adsorption of benzene derivatives and gas molecules.

Biomimetic catalytic oxidative coupling of thiols using thiolate-bridged dinuclear metal complexes containing iron in water under mild conditions

A green approach to disulfides via aerobic oxidative coupling of thiols was developed with a thiolate-bridged heteronuclear complex in water.

Linearly Polarized UV Light-Induced Optical Anisotropy of PVA Films and Flexible Macrocycle Schiff Base Ni(II), Cu(II), Zn(II) Dinuclear Complexes

Three dinuclear metal complexes (comprised of six-coordinated nNi2L and five-coordinated nCu2L and nZn2L) were confirmed by means of elemental analysis, UV-vis and IR spectra, and single X-ray crystal structural analysis in a spectroscopic study. The stable structures of these nNi2L, nCu2L, and nZn2L complexes in poly(vinylalcohol) (PVA) films were analyzed using UV-vis spectra. The molecular orientation of hybrid PVA film materials after linearly polarized light irradiation was analyzed to obtain the polarized spectra and dichroic ratio. Among the three materials, nNi2L and nZn2L complexes indicated an increasing optical anisotropy that depended on the flexibility of the complexes. We have included a discussion on the formation of the pseudo-crystallographic symmetry of the components in a soft matter (PVA films).

Quantitative Assessment of rPM6 for Fluorine- and Chlorine-Containing Metal Complexes: Comparison with Experimental, First-Principles, and Other Semiempirical Results

We report a reparameterization of PM6 parameters for fluorine and chlorine using our training set containing transition metal complexes. Spin unrestricted calculations with the resulting rPM6 (UrPM6) were examined quantitatively using two test sets: (i) the description of magnetic interactions in 25 dinuclear metal complexes and (ii) the prediction of barrier heights and reaction energies for epoxidation and fluorination reactions catalyzed by high-valent manganese-oxo species. The conventional UPM6 and UPM7 methods were also evaluated for comparison on the basis of either experimental or computational (the UB3LYP/SVP level) outcomes. The merits of UrPM6 are highlighted by both the test sets. As regards magnetic exchange coupling constants, the UrPM6 method had the smallest mean absolute errors from the experimental data (19 cm−1), followed by UPM7 (119 cm−1) and UPM6 (373 cm−1). For the epoxidation and fluorination reactions, all of the transition state searches were successful using UrPM6, while the success rates obtained by UPM6 and UPM7 were only 50%. The UrPM6-optimized stationary points also agreed well with the reference UB3LYP-optimized geometries. The accuracy for estimating reaction energies was also greatly remedied.

7-Methyl-6-furylpurine forms dinuclear metal complexes with N3,N9 coordination

Two dinuclear metal complexes bearing the purine derivative 7-methyl-6-furylpurine (1b) as a ligand are reported. In [Ag2(1b)2(DMSO)2](ClO4)2·DMSO and [Cu2(1b)2(NO3)2], two bridging purine derivatives coordinate the two metal ions via their N3 and N9 positions. In the silver(I) complex, the coordination environment of each metal ion is completed by a DMSO ligand, whereas an additional nitrato ligand coordinates to each copper(I) ion. The intramolecular Ag···Ag distance of 3.1069(5) Å is in agreement with the presence of a weak argentophilic interaction, whereas the Cu···Cu distance of 2.9382(4) Å is too long to be indicative of a cuprophilic interaction. The compounds represent the first examples of dinuclear complexes comprising two N3,N9-bridging purine derivatives without any additional bridging ligand.