We propose a simple method for predicting the spin state of homoleptic complexes of the Fe(II) d ion with chelating diimine ligands. The approach is based on the analysis of a single metric parameter within a free (noncoordinated) ligand: the interatomic separation between the N-donor metal-binding sites. An extensive analysis of existing complexes allows the determination of critical N···N distances that dictate the regions of stability for the high-spin and low-spin complexes, as well as the intermediate range in which the magnetic bistability (spin crossover) can be observed. The prediction has been tested on several complexes that demonstrate the validity of our method.
Reported is the synthesis, characterization, and material properties of the first π-conjugated two-dimensional covalent organic radical framework (CORF), PTM-CORF, based on the stable polychlorotriphenylmethyl (PTM) radical. The covalent organic framework (COF) precursor (PTM-H-COF) was first synthesized by liquid/liquid interfacial acetylenic homocoupling of a triethynylpolychlorotriphenylmethane monomer, and showed crystalline features with a hexagonal diffraction pattern matching that of A-B-C stacking. Subsequent deprotonation and oxidation of the PTM units in PTM-H-COF gave PTM-CORF. Magnetic measurements revealed that the neighboring PTM radicals in the PTM-CORF are anti-ferromagnetically coupled each other, with a moderate exchange interaction (J=-375 cm ). The PTM-CORF has a small energy gap (ca. 0.88 eV) and a low-lying LUMO energy level (-4.72 eV), and exhibits high electrocatalytic activity and durability toward the oxygen reduction reaction.
Wu and colleagues describe the challenging synthesis and physical characterization of a macrocyclic octaradicaloid and decaradicaloid. They exhibit the long-sought-after ''annulene-within-an-annulene'' super-ring structure and unusual global aromaticity with individual inner and outer rings following Hü ckel's rule in the singlet state and Baird's rule in the triplet state, respectively.
Wu and colleagues describe the challenging synthesis and physical characterizations of a series of soluble and stable rylene ribbon molecules with record length, which can serve as good model compounds of the narrowest armchair graphene nanoribbon. They observed very unusual open-shell diradical character for long rylene molecules, which can be correlated to the potential metallic property of the infinite polyrylene ribbon.
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