Optical Properties of Monolayer-Protected Aluminum Clusters: Time-Dependent Density Functional Theory Study

2015

We examine the electronic and optical properties of experimentally known monolayer-protected aluminum clusters Al4(C5H5)4, Al50(C5Me5)12, and Al69(N(SiMe3)2)183– using time-dependent density functional theory. By comparing Al4(C5H5)4 and the theoretical Al4(N(SiMe3)2)4 cluster, we observe significant changes in the optical absorption spectra caused by different hybridization between metal core and ligands. Using these initial observations, we explain the calculated spectra of Al50(C5Me5)12 and Al69(N(SiMe3)2)183–. Al50(C5Me5)12 shows a structured spectrum with clear regions of low-intensity core-to-core transitions followed by high-intensity ligand-to-core transitions due to its high symmet…

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

2015

Chemistry that uses metalloid tin clusters as a start- ing material is of fundamental interest towards understand- ing 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 differ- ent countercations. Besides the structural charact…

UV photoexcitation of a dissolved metalloid Ge9 cluster compound and its extensive ultrafast response.

2015

Femtosecond pump-probe absorption spectroscopy in tetrahydrofuran solution has been used to investigate the dynamics of a metalloid cluster compound {Ge9[Si(SiMe3)3]3}(-). Upon UV photoexcitation, the transients in the near-infrared spectral region showed signatures reminiscent of excess electrons in THF (bound or quasi-free) whereas in the visible part excited state dynamics of the cluster complex dominates.

Innenrücktitelbild: Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles (Angew. Chem. 28/2015)

2015

Single Crystal Sub‐Nanometer Sized Cu6(SR)6 Clusters: Structure, Photophysical Properties, and Electrochemical Sensing

2016

Organic ligand-protected metal nanoclusters have attracted extensively attention owing to their atomically precise composition, determined atom-packing structure and the fascinating properties and promising applications. To date, most research has been focused on thiol-stabilized gold and silver nanoclusters and their single crystal structures. Here the single crystal copper nanocluster species (Cu6(SC7H4NO)6) determined by X-ray crystallography and mass spectrometry is presented. The hexanuclear copper core is a distorted octahedron surrounded by six mercaptobenzoxazole ligands as protecting units through a simple bridging bonding motif. Density functional theory (DFT) calculations provide…

Inside Back Cover: Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles (Angew. Chem. Int. Ed. 28/2015)

2015

Atomistic Insights into Nitrogen-Cycle Electrochemistry: A Combined DFT and Kinetic Monte Carlo Analysis of NO Electrochemical Reduction on Pt(100)

2017

Electrocatalytic denitrification is a promising technology for the removal of NOx species in groundwater. However, a lack of understanding of the molecular pathways that control the overpotential and product distribution have limited the development of practical electrocatalysts, and additional atomic-level insights are needed to advance this field. Adsorbed NO has been identified as a key intermediate in the NOx electroreduction network, and the elementary steps by which it decomposes to NH4+, N2, NH3OH+, or N2O remain a subject of debate. Herein, we report a combined density functional theory (DFT) and kinetic Monte Carlo (kMC) study of this reaction on Pt(100), a catalytic surface that i…

Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles

2015

The mechanism of nitric oxide electroreduction on Pt(111) is investigated using a combination of first principles calculations and electrokinetic rate theories. Barriers for chemical cleavage of N-O bonds on Pt(111) are found to be inaccessibly high at room temperature, implying that explicit electrochemical steps, along with the aqueous environment, play important roles in the experimentally observed formation of ammonia. Use of explicit water models, and associated determination of potential-dependent barriers based on Bulter-Volmer kinetics, demonstrate that ammonia is produced through a series of water-assisted protonation and bond dissociation steps at modest voltages (0.3 V). In addit…

The Role of the Anchor Atom in the Ligand of the Monolayer-Protected Au25(XR)18– Nanocluster

2015

We present a density functional theory (DFT) investigation on the role of the anchor atom and ligand on the structural, electronic, and optical properties of the anionic Au25(XR)18– nanocluster (X = S, Se, Te; R = H, CH3, and (CH2)2Ph). Substituting the anchor atom with other group 16 elements induces subtle changes in the Au–Au and Au–X bond lengths and polarization of the covalent bond. The changes in the electronic structure based on substituting both the anchor and R groups are presented through careful analysis of the density of states and theoretical determined optical spectra. We give a detailed side-by-side comparison into the structural, electronic, and optical properties of Au25(X…

Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups

2018

Reducing (Ph3P)AuSC(SiMe3)3 with L-Selectride® gives the medium-sized metalloid gold cluster Au70S20(PPh3)12. Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of Au70S20(PPh3)12, but also behave as electron acceptors leading to auride-like gold atoms on the exterior.

CCDC 1044696: Experimental Crystal Structure Determination

2015

Related Article: Claudio Schrenk, Birgit Gerke, Rainer Pöttgen, Andre Clayborne, Andreas Schnepf|2015|Chem.-Eur.J.|21|8222|doi:10.1002/chem.201500550

CCDC 1963049: Experimental Crystal Structure Determination

2019

Related Article: Xiaohui Gao, Shuijian He, Chunmei Zhang, Cheng Du, Xi Chen, Wei Xing, Shengli Chen, Andre Clayborne, Wei Chen|2016|Adv. Sci.|3|1600126|doi:10.1002/advs.201600126

CCDC 1044697: Experimental Crystal Structure Determination

2015

Related Article: Claudio Schrenk, Birgit Gerke, Rainer Pöttgen, Andre Clayborne, Andreas Schnepf|2015|Chem.-Eur.J.|21|8222|doi:10.1002/chem.201500550