Lei-Jiao Li

All‐Metal Antiaromaticity in Sb4‐Type Lanthanocene Anions

Antiaromaticity, as introduced in 1965, usually refers to monocyclic systems with 4n π electrons. This concept was extended to all-metal molecules after the observation of Li3 Al4 (-) in the gas phase. However, the solid-phase counterparts have not been documented to date. Herein, we describe a series of all-metal antiaromatic anions, [Ln(η(4) -Sb4 )3 ](3-) (Ln=La, Y, Ho, Er, Lu), which were isolated as the K([2.2.2]crypt) salts and identified by single-crystal X-ray diffraction. Based on the results obtained from the chemical bonding analysis, multicenter indices, and the electron-counting rule, we conclude that the core [Ln(η(4) -Sb4 )3 ](3-) fragment of the crystal has three locally π-antiaromatic Sb4 fragments. This complex represents the first locally π-antiaromatic all-metal system in the solid state, which is stabilized by interactions of the three π-antiaromatic units with the central metal atom.

Particular Handedness Excess through Symmetry-Breaking Crystallization of a 3D Cobalt Phosphonate.

A 3D chiral cobalt phosphonate has been obtained from achiral precursors in the absence of chiral inducers. Remarkably, the bulk sample is largely enantio-enriched with particular handedness through symmetry-breaking crystallization in spite of multiple repeated experiments. Moreover, protonation of this chiral material introduces Brønsted acid sites, the structure of which is unique to the heterogeneous phase for the ring opening of epoxies.

Peculiar All-Metal σ-Aromaticity of the [Au2Sb16]4− Anion in the Solid State

Gas-phase clusters are deemed to be σ-aromatic when they satisfy the 4n+2 rule of aromaticity for delocalized σ electrons and fulfill other requirements known for aromatic systems. While the range of n values was shown to be quite broad when applied to short-lived clusters found in molecular-beam experiments, stability of all-metal cluster-like fragments isolated in condensed phase was previously shown to be mainly ascribed to two electrons (n=0). In this work, the applicability of this concept is extended towards solid-state compounds by demonstrating a unique example of a storable compound, which was isolated as a stable [K([2.2.2]crypt)]+ salt, featuring a [Au2 Sb16 ]4- cluster core possessing two all-metal aromatic AuSb4 fragments with six delocalized σ electrons each (n=1). This discovery pushes the boundaries of the original idea of Kekulé and firmly establishes the usefulness of the σ-aromaticity concept as a general idea for both small clusters and solid-state compounds.

[Co2@Ge16]4-: Localized vs. Delocalized Bonding in Two Isomeric Intermetalloid Clusters

We report the successful isolation and structural elucidation of two bimetallic doped [Co2 @Ge16 ]4- clusters (α and β form), which were synthesized through the reaction of [{(ArN)2 CtBu}Co(η6 -toluene)] (Ar=2,6-diisopropylphenyl) and K4 Ge9 in ethylenediamine (en) solution and co-crystallized together in [K(2,2,2-crypt)]4 [Co2 @Ge16 ]⋅en. The α-[Co2 @Ge16 ]4- isomer prefers a distinct D2h 3-connected architecture, whereas the deltahedral isomeric β-[Co2 @Ge16 ]4- isomer adopts a quasi-C2h geometry and can be seen as coupling of two distorted arachno-[Co@Ge10 ] units. Chemical bonding analyses indicate that the skeleton of the α isomer is mainly composed of localized bonds, whereas only multicenter bonding interactions govern the geometry of the β isomer, which was further found to exhibit a fluxional behavior. The coexistence of both isomers within one unit cell links the 3-connected clusters with their deltahedral congeners, thus highlighting the structural and electronic flexibility of such discreet cluster systems.

Designed Cluster Assembly of Multidimensional Titanium Coordination Polymers: Syntheses, Crystal Structure and Properties

The exploitation of new titanium-based coordination polymers (Ti CPs) with high crystallinity is difficult but highly desirable for their potential applications in photocatalysis. Herein, a cluster-cooperative assemble strategy is developed to synthesize Ti CPs. By utilizing various bifunctional ligands containing carboxylate acids and N-donor groups, we successfully assembled the zero-dimensional (0D) [(Ti3 O)(iPrO)8 ]2+ or [(Ti4 O2 )(iPrO)6 ]6+ clusters into one-dimensional (1D) tube-, ribbon-, or helical chain-shape architectures, two-dimensional (2D) layered structures, and a rare parallel 2D→three-dimensional (3D) polycatenation framework with various copper iodide dopants, including rhombus- or wing-shaped Cu2 I2 and tetrahedron- or ladder-shaped Cu4 I4 . The as-synthesized compounds display strong absorption in the visible region with narrow band gaps ranging from 1.70 to 2.72 eV and exhibit good photocatalytic activities in the degradation of organic pollutants.

Synthesis, characterization and electronic properties of an endohedral plumbaspherene [Au@Pb12]3−

We report the synthesis, characterization and DFT studies of a transition-metal-encapsulated superatom compound, [K(2,2,2-crypt)]3[Au@Pb12]·2py, which adopts a distorted symmetry instead of the icosahedral structure due to the second-order Jahn–Teller effect. DFT computations revealed its chemical bonding nature and aromatic character, and assigned the formal electronic structure as [Au−@Pb122−]3−.