0000000001090186
AUTHOR
Sami Kaappa
Patterning of supported gold monolayers via chemical lift-off lithography
The supported monolayer of Au that accompanies alkanethiolate molecules removed by polymer stamps during chemical lift-off lithography is a scarcely studied hybrid material. We show that these Au–alkanethiolate layers on poly(dimethylsiloxane) (PDMS) are transparent, functional, hybrid interfaces that can be patterned over nanometer, micrometer, and millimeter length scales. Unlike other ultrathin Au films and nanoparticles, lifted-off Au–alkanethiolate thin films lack a measurable optical signature. We therefore devised fabrication, characterization, and simulation strategies by which to interrogate the nanoscale structure, chemical functionality, stoichiometry, and spectral signature of t…
The Role of Nanocrystal Symmetry in the Crossover Region from Molecular to Metallic Gold Nanoparticles
There is a wide-spread interest to design ambient-stable gold nanoparticles with tailored physico-chemical properties for applications in several areas such as plasmonics, nanomedicine, catalysis, biological imaging, sensing, and nanoelectronics. It has been known for a long time that optical response of gold nanoparticles changes drastically in a cross-over region from 150 to 250 gold atoms, from a “molecule-like” to “metallic” behavior, but insufficient knowledge of atomic structures has precluded detailed computational studies on the underlying mechanisms. Here, we analyze the electronic structure and optical and chiroptical properties of recently reported gold nanoparticles of 144, 146,…
Highly Robust but Surface-Active : An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2-bimyAuBr with NaBH4 in one pot. X-ray crystallization analysis …
Analysis of the Electronic Structure of Non-Spherical Ligand-Protected Metal Nanoclusters: The Case of a Box-Like Ag67
In this work we introduce a new strategy to investigate the electronic shell structure of ligand-protected metal nanoclusters of polyhedral core shape. The central idea is to identify the symmetry of the Kohn–Sham molecular orbitals of an atomistic structure based on their projection onto the electronic states of a jellium system with a similar shape of the background charge density. Herein, we study the connection between a reduced atomistic model of the recently reported box-like [Ag67(SR)32(PR3)8]3+ nanocluster and a jellium box consisting of 32 free electrons. With this approach, we determine the symmetry of electronic states of the metal core and identify those that are involved in the…
Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes
Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) and halides are reported. The reduction of well-defined NHC–Au–Cl complexes produces clusters comprised of an icosahedral Au13 core surrounded by a symmetrical arrangement of nine NHCs and three chlorides. X-ray crystallography shows that the clusters are characterized by multiple CH−π and π–π interactions, which rigidify the ligand and likely contribute to the exceptionally high photoluminescent quantum yields observed, up to 16.0%, which is significantly greater than that of the most luminescent ligand-protected Au13 superatom cluster. Density functional theory analysis suggests that clusters are 8-electron …
Removal of alkylthiols from gold surface : molecular dynamics simulations in density functional theory
Self-assembled monolayers (SAMs) are systems of organic compounds adsorbed onto metal or silicon, forming a dense cover on top of the substrate; the most studied system of SAMs consists of alkylthiols on gold surface. In 2012, Liao et al. found out, as a side-product of their chemical lift-off lithography research, that when the thiol cover was pulled off the gold surface, a layer of gold was also removed from the substrate. In our study, this process was simulated using density functional theory (DFT) within projector augmented-wave (PAW) method to examine the dynamics at the interface of gold and the thiol cover. According to our results, acquired using the linear combination of atomic or…
Analysis of the Electronic Structure of Non-Spherical Ligand-Protected Metal Nanoclusters : The Case of a Box-Like Ag67
In this work we introduce a new strategy to investigate the electronic shell structure of ligand-protected metal nanoclusters of polyhedral core shape. The central idea is to identify the symmetry of the Kohn–Sham molecular orbitals of an atomistic structure based on their projection onto the electronic states of a jellium system with a similar shape of the background charge density. Herein, we study the connection between a reduced atomistic model of the recently reported box-like [Ag67(SR)32(PR3)8]3+ nanocluster and a jellium box consisting of 32 free electrons. With this approach, we determine the symmetry of electronic states of the metal core and identify those that are involved in the…
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e.,…
Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions
Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand-metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper-hydride nanocluster [Cu25H10(SPhCl2)18]3- that readily catalyzes hydrogen…
Real-space imaging with pattern recognition of a ligand-protected Ag374 nanocluster at sub-molecular resolution
High-resolution real-space imaging of nanoparticle surfaces is desirable for better understanding of surface composition and morphology, molecular interactions at the surface, and nanoparticle chemical functionality in its environment. However, achieving molecular or sub-molecular resolution has proven to be very challenging, due to highly curved nanoparticle surfaces and often insufficient knowledge of the monolayer composition. Here, we demonstrate sub-molecular resolution in scanning tunneling microscopy imaging of thiol monolayer of a 5 nm nanoparticle Ag374 protected by tert-butyl benzene thiol. The experimental data is confirmed by comparisons through a pattern recognition algorithm t…
Point Group Symmetry Analysis of the Electronic Structure of Bare and Protected Metal Nanocrystals
The electronic structures of a variety of experimentally identified gold and silver nanoclusters from 20 to 246 atoms, either unprotected or protected by several types of ligands, are characterized by using point group specific symmetry analysis. The delocalized electron states around the HOMO-LUMO energy gap, originating from the metal s-electrons in the cluster core, show symmetry characteristics according to the point group that describes best the atomic arrangement of the core. This indicates strong effects of the lattice structure and overall shape of the metal core to the electronic structure, which cannot be captured by the conventional analysis based on identification of spherical a…
Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes
Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) are reported. The reduction of well-defined NHC–Au–Cl complexes produces clusters com-prised of an icosahedral Au13 core surrounded by a symmetrical arrangement of 9 NHCs and 3 chlorides. X-ray crystallography shows that the clusters are characterized by multiple CH–π and π–π interactions, which rigidify the ligand and likely con-tribute to the exceptionally high photoluminescent quantum yields observed, up to 16.0 %, which is significantly greater than the most luminescent ligand-protected Au13 superatom cluster. Density functional theory analysis suggests that clus-ters are 8-electron superatoms with a wide …
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e.,…
Highly Robust but Surface-Active: N-Heterocyclic Carbene-Stabilized Au25 Nanocluster as a Homogeneous Catalyst
<div> <div> <div> <p>Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Herein, we report a novel N-heterocyclic carbine-stabilized Au25 nanocluster with high thermal and air stabilities as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=diisopropyl-benzilidazolium) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2- bimyAuBr with NaBH4 in o…
Highly Robust but Surface‐Active: An N‐Heterocyclic Carbene‐Stabilized Au 25 Nanocluster
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25 (i Pr2 -bimy)10 Br7 ]2+ (i Pr2 -bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2 Cl and i Pr2 -bimyAuBr with NaBH4 in one pot. X-ray crystallization…
CCDC 1521591: Experimental Crystal Structure Determination
Related Article: Mohammad J. Alhilaly, Megalamane S. Bootharaju, Chakra P. Joshi, Tabot M. Besong, Abdul-Hamid Emwas, Rosalba Juarez-Mosqueda, Sami Kaappa, Sami Malola, Karim Adil, Aleksander Shkurenko, Hannu Häkkinen, Mohamed Eddaoudi, and Osman M. Bakr|2016|J.Am.Chem.Soc.|138|14727|doi:10.1021/jacs.6b09007
CCDC 1851619: Experimental Crystal Structure Determination
Related Article: Cunfa Sun, Nisha Mammen, Sami Kaappa, Peng Yuan, Guocheng Deng, Chaowei Zhao, Juanzhu Yan, Sami Malola, Karoliina Honkala, Hannu Häkkinen, Boon K. Teo, Nanfeng Zheng|2019|ACS Nano|13|5975|doi:10.1021/acsnano.9b02052
CCDC 1886732: Experimental Crystal Structure Determination
Related Article: Mina R. Narouz, Shinjiro Takano, Paul A. Lummis, Tetyana I. Levchenko, Ali Nazemi, Sami Kaappa, Sami Malola, Goonay Yousefalizadeh, Larry A. Calhoun, Kevin G. Stamplecoskie, Hannu H��kkinen, Tatsuya Tsukuda, Cathleen M. Crudden|2019|J.Am.Chem.Soc.|141|14997|doi:10.1021/jacs.9b07854
CCDC 1916156: Experimental Crystal Structure Determination
Related Article: Hui Shen, Guocheng Deng, Sami Kaappa, Tongde Tan, Ying-Zi Han, Sami Malola, Shui-Chao Lin, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2019|Angew.Chem.,Int.Ed.|58|17731|doi:10.1002/anie.201908983