Carboxylato (R = (t)Bu and Et) and carbonato bridges have been utilized for nickel(II)-based aggregates [Ni4(μ-H2L)2(μ3-OH)2(μ1,3-O2CBu(t))2](NO3)2·H2O·2DMF (1·H2O·2DMF), Ni4(μ-(hy)HL)2(μ3-OMe)2(μ1,1-N3)2(μ1,3-O2CEt)2]·4H2O (2·4H2O), and Ni6(μ4-L)(μ3-L)2(μ6-CO3)(H2O)8](ClO4)·9H2O (3·9H2O). Building blocks [Ni2(μ-H2L)](3+), [Ni2(μ-(hy)HL)](3+), and [Ni2(μ-L)](+) originating from [Ni2(μ-H2L)](3+) have been trapped in these complexes. The complexes have been characterized by X-ray crystallography, magnetic measurements, and density functional theory (DFT) analysis. In 1, the magnetic interactions are transmitted through the μ3-phenoxido/μ3-hydroxido/syn-syn-(t)BuCO2(-), μ3-phenoxido/μ3- hydroxido, and double μ3-phenoxido/double μ3-hydroxido bridges with J = +11.4 cm(-1), J1 = -2.1 cm(-1), and J2 = -2.8 cm(-1), respectively. In 2, the interactions are ferromagnetic, with J1 = +27.5 cm(-1), J2 = +20.62 cm(-1), and J3 = +1.52 cm(-1) describing the magnetic couplings through the μ-phenoxidoo/μ3-methoxido, μ-azido/μ3-methoxido, and μ3-methoxido/μ3-methoxido exchange pathways, respectively. Complex 3 gives J1 = -3.30 cm(-1), J2 = +1.7 cm(-1), and J3 = -12.8 cm(-1) for exchange pathways mediated by μ-phenoxido/μ-carbonato, μ-alkoxido/μ-alkooxido/μ-syn-syn-carbonato, and the μ-phenoxido/μ-carbonato, respectively. Interestingly, 1 and 3 below 20 K and 35 K, respectively, show an abrupt increase of the χMT product to reach a magnetic-field-dependent maximum, which is associated with a slightly frequency-dependent out-of-phase alternating-current peak. DFT calculations have also been performed on 1-3 to explain the exchange interaction mechanisms and to support the magnitude and sign of the magnetic coupling constants between the Ni(II) ions.

The self-assembly of C-symmetric tetrapyridyl metalloligands containing Fe or Co and diruthenium electron acceptors by means of dative coordination bonding led to the formation of six different heterobimetallic supramolecules. All complexes were characterized by X-ray crystallography, ESI mass spectrometry, and H NMR (in the case of diamagnetic systems) spectroscopy. The bridging units in the diruthenium complexes greatly influenced the geometrical preference of the supramolecular structures, resulting in the formation of different architectures, namely AD or AD (A = acceptor, D = donor). Depending on the bridging unit, AD tetragonal prism, AD molecular tweezer, or AD triple-decker complexes were obtained selectively. The self-assembly of an unexpected triple-decker type RuFe heterobimetallic species was also observed.

The reaction of SIPr, [1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene] (1), with C6F6 led to the formation of an unprecedented mesoionic compound (2). The formation of 2 is made accessible by deprotonation of the SIPr backbone with simultaneous elimination of HF. The C−F bond para to the imidazolium ring in 2 is only of 1.258(4) Å, which is the one of the shortest structurally authenticated C−F bonds known to date. The liberation of HF during the reaction is unequivocally proved by the addition of one more equivalent of SIPr, which leads to the imidazolium salt with the HF2− anion. To functionalize 2, the latter reacted with B(C6F5)3 to give an unusual donor–acceptor compound, where the fluoride atom from the C6F5 moiety coordinates to B(C6F5)3 and the carbanion moiety remains unaffected. Such coordination susceptibility of the fluoride atom of a nonmetallic system to a main‐group Lewis acid (Fnon‐metal→BR3) is quite unprecedented.

Syntheses, crystal structures, magnetic properties and catechol oxidation behavior are presented for [Mn3] and [Mn4] aggregates, [MnMn(II)(O2CMe)4(dmp)2(H2O)2]·2H2O (1·2H2O), [MnMn(II)(O2CCH2Cl)4(dmp)2(H2O)2]·H2O·MeOH (2·H2O·MeOH), [Mn(μ3-O)(dmp)4(μ-DMSO)(N3)(DMSO)(H2O)]ClO4·DMSO (3·ClO4·DMSO), and [Mn(μ3-O)(dmp)4(μ-DMSO)(ClO4)(DMSO)(H2O)]ClO4·DMSO (4·ClO4·DMSO), developed with single type ligand H2dmp, 2-[(2-hydroxy-1,1-dimethyl-ethylimino)-methyl]-phenol. The successful isolation of 1-4 resulted from a systematic exploration of the effect of Mn(II) salts, added carboxylates, Mn/H2dmp ratio, presence of azide, and other reaction conditions. The cores of 1 and 2 are similar and consist of a linear Mn(III)Mn(II)Mn(III) unit in a carboxylate and H2dmp environment, revealing a central Mn(II) ion in a different environment and terminal Mn(III) ions available for the introduction of structural and magnetic anisotropy to the system. The cores of 3 and 4 are also similar and consist of a distorted incomplete-adamantane type Mn4 coordination assembly in a carboxylate-free environment built on a triangular [Mn(μ3-O)] unit. The magnetic behavior of complexes 1-3 is dominated by antiferromagnetic exchange coupling that results in ground state spin values of S = 3/2 for 1 and 2 and S = 0 for 3. In solution, all four complexes 1-4 show catechol oxidation activity towards 3,5-DTBC. The catalytic activity for the oxidation of 3,5-DTBC in air followed the order 4 < 3 < 1 < 2.