Influence of Donor-Acceptor Distance Variation on Photoinduced Electron and Proton Transfer in Rhenium(I)-Phenol Dyads

A homologous series of four molecules in which a phenol unit is linked covalently to a rhenium(I) tricarbonyl diimine photooxidant via a variable number of p-xylene spacers (n = 0–3) was synthesized and investigated. The species with a single p-xylene spacer was structurally characterized to get some benchmark distances. Photoexcitation of the metal complex in the shortest dyad (n = 0) triggers release of the phenolic proton to the acetonitrile/water solvent mixture; a H/D kinetic isotope effect (KIE) of 2.0 ± 0.4 is associated with this process. Thus, the shortest dyad basically acts like a photoacid. The next two longer dyads (n = 1, 2) exhibit intramolecular photoinduced phenol-to-rhenium electron transfer in the rate-determining excited-state deactivation step, and there is no significant KIE in this case. For the dyad with n = 1, transient absorption spectroscopy provided evidence for release of the phenolic proton to the solvent upon oxidation of the phenol by intramolecular photoinduced electron transfer. Subsequent thermal charge recombination is associated with a H/D KIE of 3.6 ± 0.4 and therefore is likely to involve proton motion in the rate-determining reaction step. Thus, some of the longer dyads (n = 1, 2) exhibit photoinduced proton-coupled electron transfer (PCET), albeit in a stepwise (electron transfer followed by proton transfer) rather than concerted manner. Our study demonstrates that electronically strongly coupled donor–acceptor systems may exhibit significantly different photoinduced PCET chemistry than electronically weakly coupled donor–bridge–acceptor molecules

Interface-engineered templates for molecular spin memory devices

The use of molecular spin state as a quantum of information for storage, sensing and computing has generated considerable interest in the context of next-generation data storage and communication devices(1, 2), opening avenues for developing multifunctional molecular spintronics(3). Such ideas have been researched extensively, using single-molecule magnets(4, 5) and molecules with a metal ion(6) or nitrogen vacancy(7) as localized spin-carrying centres for storage and for realizing logic operations(8). However, the electronic coupling between the spin centres of these molecules is rather weak, which makes construction of quantum memory registers a challenging task(9). In this regard, delocalized carbon-based radical species with unpaired spin, such as phenalenyl(10), have shown promise. These phenalenyl moieties, which can be regarded as graphene fragments, are formed by the fusion of three benzene rings and belong to the class of open-shell systems. The spin structure of these molecules responds to external stimuli(11, 12) (such as light, and electric and magnetic fields), which provides novel schemes for performing spin memory and logic operations. Here we construct a molecular device using such molecules as templates to engineer interfacial spin transfer resulting from hybridization and magnetic exchange interaction with the surface of a ferromagnet ; the device shows an unexpected interfacial magnetoresistance of more than 20 per cent near room temperature. Moreover, we successfully demonstrate the formation of a nanoscale magnetic molecule with a well-defined magnetic hysteresis on ferromagnetic surfaces. Owing to strong magnetic coupling with the ferromagnet, such independent switching of an adsorbed magnetic molecule has been unsuccessful with single-molecule magnets(13). Our findings suggest the use of chemically amenable phenalenyl-based molecules as a viable and scalable platform for building molecular-scale quantum spin memory and processors for technological development

Synthesis and Crystal Structure of a Copper(II) Benzoate Complex Bearing a Bis-2,2′-Tetrahydrofuryl Peroxide Moiety

Complex [Cu2(ben)4·2THF−(η1–O2)]∞ (2) (ben=C6H5CO2− benzoate; THF=tetrahydrofuran) was isolated when a solution of Cu2(ben)4·2THF (1) in THF upon natural sunlight irradiation yields crystals suitable for single-crystal X-ray diffraction analysis. 2, crystallized in the C2/c monoclinic space group, Z=8, V=3394.2 (4) Å3, and the unit cell parameters a=9.7935(7) Å, b=19.0055 (13) Å, c=18.2997 (13) Å, α=90°, β=94.7996 (11)º and γ=90°. This is the first example of a polymeric copper(II) carboxylate compound stabilizing a peroxo group via its apical ligand (THF molecule). Additionally, 2 was also characterized by elemental analysis, Fourier-transformed infrared spectroscopy (FTIR) and Raman spectroscopyUniversidad de Costa Rica/[804-B7-279]/UCR/Costa RicaUniversidad de Costa Rica/[804-B0-650]/UCR/Costa RicaUCR::Vicerrectoría de Docencia::Ciencias Básicas::Facultad de Ciencias::Escuela de QuímicaUCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro de Investigación en Electroquímica y Energía Química (CELEQ