Electrophilic activation and subsequent reduction of substrates is in general not possible because highly Lewis acidic metals lack access to multiple redox states. Herein, we demonstrate that transition metal-like redox processes and electronic structure and magnetic properties can be imparted to aluminum(III). Bis(iminopyridine) complexes containing neutral, monoanionic, and dianionic iminopyridine ligands (IP) have been characterized structurally and electronically; yellow (IP)AlCl(3) (1), deep green (IP(-))(2)AlCl (2) and (IP(-))(2)Al(CF(3)SO(3)) (3), and deep purple [(IP(2-))Al](-) (5) are presented. The mixed-valent, monoradical complex (IP(-))(IP(2-))Al is unstable toward C-C coupling, and [(IP(2-))Al](2-)(μ-IP-IP)(2-) (4) has been isolated. Variable-temperature magnetic susceptibility and EPR spectroscopy measurements indicate that the biradical character of the ligand-based triplet in 2 is stabilized by strong antiferromagnetic exchange coupling mediated by aluminum(III): J = -230 cm(-1) for Ĥ = -2J(Ŝ(L(1))·Ŝ(L(2))). Coordination geometry-dependent (IP(-))-(IP(-)) communication through aluminum(III) is observed electrochemically. The cyclic voltammogram of trigonal bipyramidal 2 displays successive ligand-based oxidation events for the two IP(1-/0) processes, at -0.86 and -1.20 V vs SCE. The 0.34 V spacing between redox couples corresponds to a conproportionation constant of K(c) = 10(5.8) for the process (IP(-))(2)AlCl + (IP)(2)AlCl → 2(IP(-))(IP)AlCl consistent with Robin and Day Class II mixed-valent behavior. Tetrahedral 5 displays localized, Class I behavior as indicated by closely spaced redox couples. Furthermore, CV's of 2 and 5 indicate that changes in the coordination environment of the aluminum center shift the potentials for the IP(1-/0) and IP(2-/1-) redox couples by up to 0.9 V.

Creating allotropes and polymorphs of nanoparticles (NPs) has gained tremendous momentum in recent times. Group 14 (C, Si, Ge) has a number of allotropes; some with significant applications. Here we report the synthesis of Si NPs crystallizing in the BC8 structure via a colloidal route for the first time. The BC8 structure is a metastable structure of Si that can be accessed from the β-Sn form through the release of high pressure. These Si BC8 structured NPs were synthesized via reduction of SiI4 with n-butyllithium, capped with octanol and precipitated from solution. The transmission electron microscopy lattice fringes as well as the selected area electron diffraction pattern of the precipitate are consistent with the BC8 structure. The LeBail whole profile fitting of powder X-ray diffraction data also confirms the structure as the BC8 phase. The Raman spectrum provides further evidence to support the BC8 structure. With proper tuning of the band gap these NPs could be potential candidates for solar cells.

We report the synthesis, structure, and magnetic properties of a new Zintl phase and structure type, Eu11Zn4Sn2As12. The structure and composition of this phase have been established by single-crystal X-ray diffraction and electron microprobe analysis. Eu11Zn4Sn2As12 crystallizes in monoclinic space group C2/c (No. 15) with the following lattice parameters: a = 7.5679(4) Å, b = 13.0883(6) Å, c = 31.305(2) Å, and β = 94.8444(7)° [R 1 = 0.0398; wR 2 = 0.0633 (all data)]. The anisotropic structural features staggered ethane-like [Sn2As6]12– units and infinite ∞ 2[Zn2As3]5– sheets extended in the a–b plane. Eu cations fill the space between these anionic motifs. Temperature-dependent magnetic properties and magnetoresistance of this Zintl phase have been studied, and the electronic structure and chemical bonding were elucidated using first-principles quantum chemical calculations (TB-LMTO-ASA). Quantum chemical calculations show that the ethane-like units can be considered as consisting of covalent single bonds; however, the ∞ 2[Zn2As3]5– sheets are best described with delocalized bonding and there is evidence of Eu–As interactions. Temperature-dependent magnetization and transport properties between 2 and 300 K show a ferromagnetic transition at 15 K, a band gap of 0.04 eV, and negative colossal magnetoresistance.

The synthesis and transport properties of the family of coinage metal-stuffed Zintl compounds, Eu9Cd4–x CM2+x–y □ y Sb9 (CM = coinage metal, □ = vacancies), is presented as a function of coinage metal substitution. Eu9Cd4–x CM2+x–y □ y Sb9 compounds are shown to be rare examples of metallic Zintl phases with low thermal conductivities. While the lattice thermal conductivity is low, which is attributed to the complex structure and presence of interstitials, the electronic contribution to thermal conductivity is also low. In these p-type compounds, the carriers transmit less heat than expected, based on the Wiedemann–Franz law and metallic conduction, κ e = L 0 T/ρ. Density functional theory (DFT) calculations indicate that the Fermi level resides in a pseudo-gap, which is consistent with the metallic description of the properties. While the contribution from the interstitial CM states to the Fermi level is small, the interstitial CMs are required to tune the position of the Fermi level. Analysis of the topology of electron localization function (ELF) basins reveals the multicenter Eu−Cd­(CM)−Sb interactions, as the Eu and Sb states have the largest contribution at the top of the valence band. Regardless of the success of the Zintl concept in the rationalization of the properties, the representation of the CM-stuffed Eu9Cd4Sb9 structure as Eu cations encapsulated into a polyanionic (Cd/Cu)Sb network is oversimplified and underestimates the importance of the Eu–Sb bonding interactions. These results provide motivation to search for more efficient thermoelectric materials among complex metallic structures that can offer less electronic thermal conductivity without deteriorating the electrical conductivity.

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