Modulation of Charge Distribution in Cobalt-α-Diimine Complexes toward Valence Tautomerism.

Valence tautomerism (VT) and spin crossover (SCO) are promising avenues for developing a range of molecular materials for sensing, memory, and optoelectronic applications. However, these phenomena arise only when specific metal-ligand combinations are employed. The underexplored combination of cobalt(II/III) paired with bis((aryl)imino)acenapthene (Ar-BIAN) ligands, which can exist as neutral Ar-BIAN0 (L0), monoanionic radical Ar-BIAN•- (L•-), and dianionic Ar-BIAN2- (L2-) forms, has potential to afford both VT and SCO. Aiming to develop a new family of switchable molecules, we systematically explored a dual-tuning approach by varying the redox state and aryl substituents in a series of homoleptic [Co(Ar-BIAN)3]n+ complexes (Ar = Ph, n = 2 (12+), 1 (1+), 0 (1); Ar = 3,5-CF3-Ph, n = 0 (2); Ar = 4-MeO-Ph, n = 2 (32+), 0 (3)). As a prelude to synthetic and experimental studies, density functional theory (DFT) calculations were used to explore the structure and relative energies of the different electronic forms of each complex, comprising different cobalt oxidation and spin states and different ligand oxidation states. Except for compound 3, DFT identified a HS-CoII-L0 containing ground state for all complexes, precluding thermally induced SCO or VT. For 3, calculations suggested a possible thermally accessible LS-CoIII-(L•-)3 ⇌ HS-CoII-(L•-)2(L0) VT interconversion. Experimentally, structural and magnetic data reveal a HS-CoII-L0 containing ground state for all six compounds in the solid state, including 3, discounting thermally induced VT or SCO. In solution, electrochemical and spectroscopic analysis also indicate that all compounds exist as the HS-CoII-L0-containing electromer at 298 K. Intervalence charge transfer (IVCT) bands observed for neutral 1, 2, and 3 at room temperature suggest the mixed-valence HS-CoII-(L•-)2(L0) charge distribution. However, cooling 3 to 243 K in acetonitrile uniquely affords a substantial reduction in the intensity of this IVCT band, consistent with thermally induced VT interconversion to the LS-CoIII-(L•-)3 ground state as predicted by DFT calculations. This study emphasizes the utility of computationally guided molecular design for complicated systems with redox activity at the metal and multiple ligands, thus opening new avenues for tuning electronic structure and developing new families of switchable molecules.

Redox-Addressable Single-Molecule Junctions Incorporating a Persistent Organic Radical.

Integrating radical (open-shell) species into non-cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open-shell character is generally lost in contact with the metallic electrodes. Herein, single-molecule devices incorporating a 6-oxo-verdazyl persistent radical have been fabricated using break-junction techniques. The open-shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed-shell anionic state in a single-molecule transistor configuration. Furthermore, electronically driven rectification arises from bias-dependent alignment of the open-shell resonances. The integration of radical character, transistor-like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open-shell species.

Poor sperm quality and advancing age are associated with increased sperm DNA damage in infertile men.

With increasing evidence for faulty paternal contribution to reproduction, there has been a steady increase in studies highlighting an association between sperm DNA damage, failed/delayed fertilisation and aberrant embryo development. Owing to prevailing ambiguity, the aims of the study were to analyse the genetic integrity of the male gamete and then to understand its association with age, standard semen parameters, lifestyle and occupational factors. The study included 504 subjects, attending university infertility clinic for fertility evaluation and treatment. Semen characteristics were analysed by standard criteria; terminal deoxynucelotidyl transferase-mediated nick end-labelling assay was employed for DNA damage assessment. The average incidence of sperm DNA damage in patients with normozoospermic semen parameters was <10%. Patients with oligozoospermia, severe oligozoospermia, oligoasthenoteratospermia, asthenoteratozoospermia and necrozoospermia had significantly higher level of sperm DNA damage (P < 0.001). Patients above 40 years of age had significantly high levels of DNA damage (P < 0.001) compared with their counterparts. Patients with varicocele and a history of alcohol consumption had higher incidence of spermatozoa with DNA damage (P < 0.01). Poor sperm characteristics in the ejaculate are associated with increased sperm DNA damage. Age-related increase in sperm DNA damage and association of the same with varicocele and alcohol consumption are also demonstrated.