Article
Chemistry, Multidisciplinary
Bin Lu, Karol Vegso, Simon Micky, Christian Ritz, Michal Bodik, Yuriy Myronovych Fedoryshyn, Peter Siffalovic, Andreas Stemmer
Summary: In this work, a method for fabricating large-area gold nanoparticle superlattices with subnanometer interparticle gaps is demonstrated. The electrical transport measurements reveal significant variations in the nanogap conductance, while in situ optical reflectance measurements show enhanced plasmonic capacitive coupling with decreasing interparticle gap distance. The resulting superlattices also exhibit tunable effective refractive index and extreme field confinement in the high-density subnanometer plasmonic gaps.
Article
Chemistry, Physical
Shuaipeng Chen, Shuaibin Li, Yun Wang, Quan Ren, Yuhua Feng, Hongyu Chen
Summary: We have demonstrated a method to continuously tune the wetting growth of Au on Se seed nanoparticles by manipulating the growth kinetics. This approach allows us to obtain a series of Se-Au hybrids and anisotropic Au semi-shell structures with different sizes, and enables continuous tuning of their absorptions and LSPRs within the Visible-NIR spectral range.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Nanoscience & Nanotechnology
Lulu Zhu, Yifan Wu, Sujuan Wu, Fan Dong, Jiexiang Xia, Bin Jiang
Summary: The successful incorporation of subnanometer Ag/AgCl clusters into Bi12O17Cl2 nanosheets has led to enhanced photocatalytic activity for NO removal, showing 3 times higher activity than Bi12O17Cl2 and 1.8 times higher activity than defective Bi12O17Cl2. The substitution of active sites to subnanometer Ag/AgCl clusters allows for tunable redox potential and different reaction mechanisms in NO removal, while achieving selectivity in the photoinduced redox reaction on NO oxidation and CO2 reduction by introducing an extra energy level.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Matej Bubas, Jordi Sancho-Parramon
Summary: The alloying of noble metals is being explored to tune the optical and plasmonic properties of metal nanostructures. Using a low-cost approach based on density functional theory (DFT), deep insights for tailoring noble alloy properties can be gained. The study suggests that the GLLB-SC functional is a better alternative than the commonly used PBE functional for predicting optical properties of alloyed nanoparticles, thin films, and bulk alloys.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Materials Science, Ceramics
Abhiram Jagannathan, Jagannath Gangareddy, R. Rajaramakrishna, K. M. Rajashekara, S. Venugopal Rao, J. Kaewkhao, S. Kothan, A. El-Denglawey
Summary: This study focuses on the optical properties of Au-Ag bimetallic nanoparticles doped in dichroic glasses, highlighting the importance of precursor materials (AgNO3, AgCl, and AgI). The incorporation of silver and gold in the glass matrix reduces nanoparticle size and enhances the nonlinear refractive index, with potential overlap of surface plasmon resonance of Ag and Au. Differences in bandgap energy due to different dopants impact the nonlinear optical properties of the nanoparticles.
JOURNAL OF NON-CRYSTALLINE SOLIDS
(2021)
Article
Chemistry, Physical
Tomoki Matsuyama, Jun Hirayama, Yu Fujiki, Soichi Kikkawa, Wataru Kurashige, Hiroyuki Asakura, Naomi Kawamura, Yuichi Negishi, Naoki Nakatani, Keisuke Hatada, Fukiko Ota, Seiji Yamazoe
Summary: The electronic states of gold clusters are significantly influenced by different ligands, as observed through X-ray absorption spectroscopy. Differences in white-line intensity and peak positions were found between phosphine- and thiolate-protected gold clusters.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Correction
Chemistry, Physical
Marvin Treger, Adrian Hannebauer, Andreas Schneider, Jan L. Budde, Peter Behrens, Andreas M. Schneider
Summary: The optical properties of the metal-organic framework UiO-66 were tuned by ligand functionalization in this study. The research provides new insights into the optical applications of metal-organic frameworks.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yifan Wang, Ya-Qiong Su, Emiel J. M. Hensen, Dionisios G. Vlachos
Summary: Subnanometer catalysts provide high noble metal utilization and superior performance for various reactions. However, understanding their atomic-scale structures and properties under working conditions is challenging due to the large configurational space. In this study, an efficient multiscale framework integrating density functional theory (DFT) calculations, cluster expansion, machine learning, and structure optimization is introduced to predict the stability of catalysts exposed to adsorbates. The framework enables automatic discovery of stable catalyst structures and a systematic strategy to exploit properties at the subnanometer scale. Simulation results for CO-adsorbed Pd-n (n = 1-55) clusters on CeO2(111) reveal that CO can facilitate restructuring by stabilizing smaller planar structures and bilayer structures of specific intermediate sizes.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Physical
Qi-Yuan Fan, Ye Wang, Jun Cheng
Summary: Small cluster catalysts exhibit complex structural dynamic effects during catalytic reactions, with temperature significantly impacting their catalytic performance. The size of clusters also plays a crucial role in dynamic effects and sensitivity to temperature changes.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Xiaohang Wu, Ying Lv, Yuyuan Bai, Haizhu Yu, Manzhou Zhu
Summary: Density functional theory calculations were used to elucidate the mechanism of reversible single atom size conversion between [Au-10(DMPP)(4)(C6H11C C)](3+) and [Au-9(DMPP)(4)](3+). The presence or absence of the alkyne group plays a crucial role in determining the electron density of the gold core, leading to different pathways for nucleophilic or electrophilic attacks and subsequent transformations.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Krishnakanta Mondal, Arup Banerjee, Alessandro Fortunelli, Alessandro Megha
Summary: Using ab initio density functional theory, we investigated the ability of a subnanometer bimetallic Au19Pt cluster to adsorb and activate CO2 molecules in an aqueous electrochemical environment. Our study revealed that, in water, Au19Pt obtains a negative charge and selectively promotes the adsorption and activation of CO2 through electron transfer and hybridization of oxygen p-orbitals and partially filled platinum d-orbitals. Remarkably, Pt acts as a collector of negative charge and behaves as a CO2-activating single-atom catalyst embedded within a robust Au-20-like framework, suggesting the potential of Au19Pt as a candidate for CO2 mitigation.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Justin B. Patty, Shana Havenridge, Dylan Tietje-Mckinney, Maxime A. Siegler, Kundan K. Singh, Roumina Hajy Hosseini, Mohamed Ghabin, Christine M. Aikens, Anindita Das
Summary: The article reports the first example of a chiral mixed thiolate/stibine-protected gold cluster, with the chirality originating from a unique arrangement on an achiral Au-13 core. The structure and properties of this new Au-18 cluster are found to be different from other reported achiral Au-18 clusters and the only other stibine-protected [Au-13(SbPh3)(8)Cl-4](+) cluster, highlighting the importance of detailed analysis on its geometric and electronic structures for understanding its optical properties, reactivity, and stability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Benedict J. Elvers, Sebastian Paetsch, Siva S. M. Bandaru, Vera Krewald, Carola Schulzke, Christian Fischer
Summary: Heteroleptic molybdenum complexes with P2N2 and non-innocent dithiolene ligands were synthesized and electrochemically characterized. The reduction potentials of the complexes were adjusted by ligand-ligand cooperativity via non-covalent interactions. This finding was supported by electrochemical studies, UV/Vis spectroscopy, and temperature-dependent NMR spectroscopy. The observed behavior resembles enzymatic redox modulation through second ligand sphere effects.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hong Yi, Kimberly M. Osten, Tetyana Levchenko, Alex J. Veinot, Yoshitaka Aramaki, Takashi Ooi, Masakazu Nambo, Cathleen M. Crudden
Summary: A series of chiral Au-13 nanoclusters were successfully synthesized and characterized, exhibiting high luminescence and stability. This opens up opportunities for further investigation into the impact of chirality on the properties of these clusters.
Article
Chemistry, Inorganic & Nuclear
Zhuang-Hua Liu, Ran-Qi Chen, San-Tai Wang, Ya-Jie Liu, Wei-Hui Fang, Jian Zhang
Summary: The currently largest catecholato-based aluminum oxo clusters were synthesized and high nuclearity AlOCs were successfully achieved by adjusting the amount of auxiliary ligands. New compounds were obtained using imidazole ligands. The compounds exhibit manifest reverse saturation absorption response.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuting Wang, Nabin Maity, Liming Zhao, Maximilian Kramer, Jun-ya Hasegawa, Yukatsu Shichibu, Katsuaki Konishi, Xiaoyuan Wang, Zhiyi Song, Masayoshi Bando, Tamaki Nakano
Summary: 2,7-Bis(2-phenyl-1H-imidazol-4-yl)fluorenone (BPIFO) was synthesized as a new fluorenone derivative with two imidazole moieties, showing remarkable and reversible changes in photo physical properties through two-step deprotonation with a base and back protonation with an acid in dimethylsulfoxide, which were explained by DFT calculations.
Article
Chemistry, Physical
Yukatsu Shichibu, Fan Zhang, Yuxiang Chen, Masafumi Konishi, Susumu Tanaka, Hiroaki Imoto, Kensuke Naka, Katsuaki Konishi
Summary: The choice of protecting ligands in the design of ligand-protected metal clusters greatly influences the nuclearity, geometry, and electronic structures, resulting in a diverse range of cluster compounds. This study synthesized two novel diarsine-protected Au-13 clusters and compared them with diphosphine analogs in terms of core geometry and optical properties. Despite similar icosahedral Au-13 cores, subtle structural differences associated with the bridging unit of ligands led to notable differences in absorption and photoluminescence profiles.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Zhiyi Song, Hiroyasu Sato, Adriana Pietropaolo, Qingyu Wang, Shuhei Shimoda, Heshuang Dai, Yoshitane Imai, Hayato Toda, Takunori Harada, Yukatsu Shichibu, Katsuaki Konishi, Masayoshi Bando, Naofumi Naga, Tamaki Nakano
Summary: From the experiment, it is found that the CD spectral intensity of linear polyurethane is amplified through aggregate formation, while the CPL emission is not enhanced. On the other hand, the CPL emission of the cyclic dimer is largely amplified due to intermolecular excimer formation through aggregation, while the CD intensity is not affected.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Takuya Sagawa, Hirokazu Kobayashi, Chinatsu Murata, Yukatsu Shichibu, Katsuaki Konishi, Mineo Hashizume, Atsushi Fukuoka
Summary: Chitin is a rich marine biomass that can be used to produce renewable organonitrogen compounds. This study focuses on the catalytic conversion of 2-acetamide-2-deoxysorbitol (ADS) into oxazolidinones. Specifically, the isomer 2,3-OX, which possesses specific chirality suitable for antibiotic applications, was selectively obtained with a high yield using the ubiquitous base catalyst KHCO3. DFT calculations revealed that innermolecular hydrogen bonds in the transition states play a crucial role in the selective formation of 2,3-OX.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Review
Chemistry, Multidisciplinary
Yukatsu Shichibu, Katsuaki Konishi
Summary: This review introduces recent studies on the chirality of gold clusters, focusing on the geometric features of the ligand shells and the atomic-level origin of chiroptical activity. The findings from computational studies provide important insights into the chiral properties of gold clusters and can contribute to the design of chirality-controlled catalysts.
Review
Chemistry, Inorganic & Nuclear
Yuki Saito, Chinatsu Murata, Mizuho Sugiuchi, Yukatsu Shichibu, Katsuaki Konishi
Summary: This review focuses on the assembly of coordinated metal clusters, including examples of supramolecular-type assemblies and behaviors associated with ordered cluster assembly and crystal polymorphism. It also discusses recent works on 1D cluster arrays bridged by metal-metal bonds and covalently cross-linked multi-cluster systems.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Chinatsu Murata, Jaesob Shin, Katsuaki Konishi
Summary: In this paper, it is demonstrated through experiments that the polyanionic Mo132O372 cage with a hydrophobic inner nanospace has the capability to engage in anion-pi interactions, exhibiting a preference for electron-deficient mono-substituted benzenes over non-electron-deficient guests in the inclusion.
CHEMICAL COMMUNICATIONS
(2023)
Article
Materials Science, Multidisciplinary
Haru Hirai, Takuya Nakashima, Shinjiro Takano, Yukatsu Shichibu, Katsuaki Konishi, Tsuyoshi Kawai, Tatsuya Tsukuda
Summary: In this study, the effects of single-atom doping on the chiroptical properties of gold superatoms were investigated. It was found that single-atom doping can improve the chiroptical properties of gold superatoms, and this study provides a rational guide for enhancing their chiroptical activity.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Biology
Fayrouz Naim, Rie Hasebe, Shintaro Hojyo, Yukatsu Shichibu, Asuka Ishii, Yuki Tanaka, Kazuki Tainaka, Shimpei I. Kubota, Katsuaki Konishi, Masaaki Murakami
Summary: Microinflammation increases the permeability of specific blood vessels by elevating local inflammatory mediators. We developed a new three-dimensional visualization method using luminescent gold nanoclusters and the CUBIC tissue-clearing method to track the development of microinflammation and the recruitment of pathogenic immune cells at specific blood vessels.
Article
Chemistry, Multidisciplinary
Yuki Saito, Yukatsu Shichibu, Katsuaki Konishi
Summary: The covalent networks of [Au-25(SR)(18)](-) nanoclusters were synthesized using reversible disulfide linkages, facilitated by the unique capabilities of the nanoclusters to mediate oxidation processes. Studies showed that Au-25 clusters can promote the formation of intercluster disulfide linkages through O-2-mediated radical reactions. This work demonstrates the potential of ligand-protected nanoclusters in the bottom-up construction of nanomaterials.
Article
Chemistry, Multidisciplinary
Yukatsu Shichibu, Yuri Ogawa, Mizuho Sugiuchi, Katsuaki Konishi
Summary: Studying the chiroptical properties of ligand-protected gold clusters with intrinsically chiral cores, it was found that surface ligands can slightly twist the gold core to generate intrinsic chirality, contributing to the appearance of the chiroptical response. Calculated CD signals are dependent on the degree of asymmetry, providing a visual understanding of the origin of helical charge movements.
NANOSCALE ADVANCES
(2021)