[Nb@Ge13/14]3−: New Family Members of Ge-Based Intermetalloid Clusters

During the past two decades, single-atom-centered medium-sized germanium clusters [M@Ge_n] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge₁₃ and Ge₁₄ endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge₁₃]³⁻ ( 1 ) and [Nb@Ge₁₄]³⁻ ( 2 ), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1 . Low occupancies of the direct two-center two-electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency.     

Luminescent Ag6Au6 Heterometallic Ethisterone Cluster and Probe for Estrogen Receptor α

A heterometallic cluster [Ag₆Au₆(ethisterone)₁₂] of an unprecedented topology was synthesized and characterized. A sensitive and specific probe for estrogen receptor α (ERα) has been developed for the first time based on the enhancement of the Ag₆Au₆ luminescence.     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

零维到三维结构中三核铜自旋阻挫簇单元的磁构关系和反对称交换

量子自旋液体是最近几年刚被人们证实除铁磁体、反铁磁体之外的第三种磁性类型,因其有望解释高温超导的运行机制、改变计算机硬盘信息存储方式而在物理、材料等领域备受关注。自旋阻挫作为量子自旋液体的最小单元可能是解开量子自旋液体诸多问题的钥匙,所以在磁学、电学研究领域再一次成为人们研究的热点。基于文献报道的三核铜配合物[Cu3(μ3-OH)(μ-OPz)3(NO3)2(H2O)2]·CH3OH(1),我们合成了三维金属有机框架配合物{[Ag(HOPz)Cu3(μ3-OH)(NO3)3(OPz)2Ag(NO3)]·6H2O}n(2)(HOPz=甲基(2-吡嗪基)酮肟),并从自旋阻挫的角度对二者磁性质进行对比和详细分析。磁化率数据表明自旋间有很强的反铁磁相互作用和反对称交换。通过包含各向同性和反对称交换的哈密顿算符对两者磁学数据进行拟合并研究其磁构关系,所获最佳拟合参数为:配合物1:Jav=-426 cm^-1,g⊥=1.83,g∥=2.00;配合物2:Jav=-401 cm^-1,g⊥=1.85,g∥=2.00。     

Reactions with a Metalloid Tin Cluster {Sn10[Si(SiMe3)3]4}2−: Ligand Elimination versus Coordination Chemistry

Chemistry that uses metalloid tin clusters as a starting material is of fundamental interest towards understanding the reactivity of such compounds. Since we identified {Sn₁₀[Si(SiMe₃)₃]₄}^2? 7 as an ideal candidate for such reactions, we present a further step in the understanding of metalloid tin cluster chemistry. In contrast to germanium chemistry, ligand elimination seems to be a major reaction channel, which leads to the more open metalloid cluster {Sn₁₀[Si(SiMe₃)₃]₃}^? 9 , in which the Sn core is only shielded by three Si(SiMe₃)₃ ligands. Compound 9 is obtained through different routes and is crystallised together with two different countercations. Besides the structural characterisation of this novel metalloid tin cluster, the electronic structure is analysed by ¹¹⁹Sn Mössbauer spectroscopy. Additionally, possible reaction pathways are discussed. The presented first step into the chemistry of metalloid tin clusters thus indicates that, with respect to metalloid germanium clusters, more reaction channels are accessible, thereby leading to a more complex reaction system.     

Synthesis,characterization, and some electrocatalytic properties of heteromultinuclear FeI/RuII Clusters

A series of new heteromultinuclear Fe^I/Ru^II clusters are described. The complexes (η⁶-arene)RuFe₂S₂(CO)₆ (arene = p-cymene 1 , C₆Me₆ 2 ) and Fe₂[μ-S (Cp*Ru)(CO)₂]₂(CO)₆ (Cp* = η⁵-C₅Me₅) ( 3 ) were prepared by the reduction reactions of (μ-S)₂Fe₂(CO)₆ with 2 equiv of LiHBEt₃, followed by treatment (μ-SLi)₂Fe₂(CO)₆ with ruthenium-arene complexes Ru₂(μ-Cl)₂Cl₂(η⁶-arene)₂ or Cp*Ru (CO)₂Cl in 22–33% yields. Further reactions of 1 and 2 with 1 equiv of triphenylphosphine in the presence of the decarbonylating agent Me₃NO·2H₂O, afforded the corresponding monophosphine-substituted Fe^I/Ru^II complexes (η⁶-arene)RuFe₂S₂(CO)₅(Ph₃P) (arene = p-cymene 4 , C₆Me₆ 5 ) in 75% and 78% yields. While treatment of parent complex 1 or 2 with 1 equiv of diphosphine Ph₂PCH₂PPh₂ (dppm) in xylene at reflux temperature resulted in the formation of the diphosphine-bridged RuFe₂S₂(CO)₉ derivate RuFe₂S₂(CO)₇(dppm) ( 6 ). The possible pathway for the formation was proposed. Two isomers of novel macrocyclic complexes involve the (η⁶-arene) Ru-bridged quadruple-butterfly Fe/S clusters [{μ-S (CH₂)₃S-μ}{(μ-CS₂)Fe₂(CO)₆}₂]₂[(η⁶-arene)Ru]₂ (arene = p-cymene 7a and 7b , C₆Me₆ 8a and 8b ) were isolated by reactions of two μ-CS₂-containing dianion [{μ-S (CH₂)₃S-μ}{(μ-S=CS)Fe₂(CO)₆}₂]²⁻ with [Ru₂(μ-Cl)₂Cl₂(η⁶-arene)₂], in which the propylene groups are attached to two S atoms by ee and ea types of bonds respectively. All the new complexes 1 – 8 have been characterized by elemental analysis, spectroscopy, and particularly for 1 – 6 , 7b and 8a by X-ray crystallography. In addition, the electrochemical properties of representative complexes 1 – 4 and 6 have been investigated.     

Side-on-End-on Coordination of Dinitrogen on a Polynuclear Vanadium Nitride Cluster Anion [V5N5]−

The side-on-end-on coordination of N₂ can be very important to activate and functionalize this very stable molecule. However, such coordination has rarely been reported. This study reports a gas-phase species (a polynuclear vanadium nitride cluster anion [V₅N₅]⁻) that can capture N₂ efficiently (12 %), and the quantum chemistry modelling suggests an unusual side-on-end-on coordination. The cluster anions were generated by laser ablation and the reaction with N₂ has been characterized by mass spectrometry, photoelectron imaging spectroscopy, and density functional theory calculations. The back-donation interactions between the localized d–d bonding orbitals on the low-coordinated dual metal (V) sites and the antibonding π* orbitals of N₂ are the driving forces to adsorb N₂ with a high binding energy (about 2.0 eV).