Article
Chemistry, Physical
Jing Cheng, Qingqing Feng, Xingxing Li, Jinlong Yang
Summary: Cluster-assembled materials with intrinsic ferromagnetism and desirable electronic and magnetic properties are designed by utilizing a magnetic superatomic cluster [Fe6S8(CN)(6)](5-) as the building block. The properties of the 2D nanosheets can be easily modulated by electron and hole doping, and the Curie temperatures can be improved by choosing different transition metals. [NH4](3)[Fe6S8(CN)(6)]Cr is a bipolar magnetic semiconductor, while the other three ([NH4](3)[Fe6S8(CN)(6)]-TM (TM = Mn, Fe, Co) are half semiconductors.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Takaho Yokoyama, Atsushi Nakajima
Summary: With the development of gas phase nanocluster synthesis methods, atomically precise nanoclusters composed of metal and semiconductor atoms have emerged, which have various functions such as catalysts and optoelectronic materials. The exploration of stable nanoclusters, called magic number nanoclusters, has revealed important factors such as highly symmetric geometric structures and electronic shell closures. The recent development of a pulsed magnetron sputtering method enables the fabrication of superatomic assemblies and investigation of their electrical properties for the development of new functional nanoscale materials.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Rohul H. Adnan, Jenica Marie L. Madridejos, Abdulrahman S. Alotabi, Gregory F. Metha, Gunther G. Andersson
Summary: This review focuses on the unique chemistry, structure, electronic, and optical properties of gold-phosphine clusters, as well as their applications in catalysis. Gold-phosphine clusters have well-defined structures that allow for the study of structure-property relationships. The use of multidentate phosphines enables the preparation of gold clusters with exotic structures beyond regular polyhedra.
Article
Chemistry, Physical
Jie She, Wei Pei, Si Zhou, Jijun Zhao
Summary: This study explores the structural and electronic factors that govern the luminescent properties of ligand-protected metal clusters. By using time-dependent density functional theory calculations, the researchers found that the emission wavelength and fluorescence intensity of a particular gold cluster could be adjusted by substituting the central gold atom with different transition metal atoms. The study also reveals the crucial role of dopants, the gold cage, and ligands in the development of light-emitting behavior.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Alvaro Munoz-Castro
Summary: The study investigates the role of different diphenyl ligands in the formation of Au-11 core, revealing the differences in interactions with the ligands between the experimentally determined compact core and the extended core. The overall structure is mainly determined by the contributions from the ligand shell characteristics and the resulting core-ligand interactions, providing insights for designing tunable clusters for nano-structured materials.
Article
Multidisciplinary Sciences
Masahiro Shibuta, Tomoya Inoue, Toshiaki Kamoshida, Toyoaki Eguchi, Atsushi Nakajima
Summary: The authors report enhanced stability for Al-13(-) and boron-doped B@Al-12(-) on a molecularly decorated p-type organic substrate. Selection of organic molecules controls the design of assembled materials containing both Al-13(-) and boron-doped B@Al-12(-) superatomic assemblies through optimizing the cluster-surface interactions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Wei-Dan Si, Kai Sheng, Chengkai Zhang, Zhi Wang, Shan-Shan Zhang, Jian-Min Dou, Lei Feng, Zhi-Yong Gao, Chen-Ho Tung, Di Sun
Summary: This study reports the spontaneous assembly of unique P- and M-single stranded helical superstructures from R- and S-Au8c individual nanoclusters, respectively, using chiral BINAP and hydrophilic o-HMBA as ligands. The chirality of the nanoclusters is derived from the homochiral ligands and the inherently chiral Au-8 metallic kernel. The helical superstructures are formed through O-H···O interactions between (HCO3-)(2) dimers and achiral o-HMBA(-) ligands. This work provides an effective strategy to construct cluster-based helical superstructures at the atomic level and offers experimental evidence for understanding the formation mechanism of helical superstructures.
Article
Chemistry, Multidisciplinary
Wataru Ishii, Yoshinori Okayasu, Yoichi Kobayashi, Rika Tanaka, Shohei Katao, Yoshiko Nishikawa, Takuya Nakashima, Tsuyoshi Kawai
Summary: The optical property of an ionic metal nanocluster (NC) is affected by the ionic interaction with counter ions. The modification of trianionic [Ag29(BDT)12(TPP)4]3- NC with silver(I) complexes led to intense photoluminescence (PL) in the near-infrared (NIR) region. The binding of silver(I) complexes to the peripheral region of Ag29 NC is confirmed by various measurements, and the change in excited-state dynamics by the binding is discussed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Haru Hirai, Shinjiro Takano, Takuya Nakashima, Takeshi Iwasa, Tetsuya Taketsugu, Tatsuya Tsukuda
Summary: In this study, a series of MAu12(dppe)(5)Cl-2 compounds with icosahedral structures were synthesized and their electronic structures, photoluminescence, and photocatalytic properties were systematically investigated. Doping an M element at the lower left of the periodic table expanded the energy gap between HOMO and LUMO, resulting in enhanced photoluminescence quantum yield. MAu12 (M=Pt, Rh, or Ir) exhibited higher photocatalytic activity than Au-13.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Yu-Feng Liu, Ke Li, Hui-Yong Lian, Xue-Jiao Chen, Xing-Lei Zhang, Guo-Ping Yang
Summary: A novel U(VI)-containing polytungstate tetramer was synthesized and demonstrated to possess good catalytic performance in the synthesis of pyrazoles.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jianfeng Wu, Qianqian Yang, Haoyu Wang, Yan Ge, Jinkui Tang, Zhenhui Qi
Summary: The anion-adaptive self-assembly method described in the study successfully produced large single-molecule magnets and explored the influence of structural factors on magnetic properties. X-ray diffraction and magnetic investigations revealed that the resulting hexagonal metallacycle exhibited unique characteristics, behaving as a double relaxation single-molecule magnet under a dc field.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Ayan Bhattacharyya, Suman De Sarkar, Anindita Das
Summary: Visible-light-mediated photoredox catalysis has been developed as an efficient alternative to conventional organic synthesis, with researchers now incorporating supramolecular chemistry techniques to customize traditional catalysts and expand their scope through noncovalent interactions. The use of supramolecular engineering has led to improved efficiency in known chemical reactions and the development of advanced synthetic methodologies. Additionally, self-assembly strategies within confined nanospaces have been shown to impact photocatalytic reactions.
Article
Chemistry, Multidisciplinary
Zongshang Li, Ke Xiao, Qingyun Wan, Rui Tang, Kam-Hung Low, Xiaodong Cui, Chi-Ming Che
Summary: The introduction of multiple kinetic aggregation states (Aggs) into the self-assembly pathway can increase the complexity and flexibility of the self-assemblies. This was achieved by using a series of chiral and achiral d(10) Au-I bis(N-heterocyclic carbene, NHC) complexes, where the achiral complex could undergo self-assembly with multiple kinetic Aggs. The chiral Au-I self-assemblies exhibited nonlinear optical response of second harmonic generation (SHG) and could function as optical waveguides with strong emission polarization, while these properties were absent in the achiral analogue.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Nanoscience & Nanotechnology
Jindiao Wu, Jianan Zhang, Yanjun Liu, Jun Wang, Cheng Zhang, Jiatao Yan, Wen Li, Toshio Masuda, Andrew K. Whittaker, Afang Zhang
Summary: Molecules with C-3 symmetry can self-assemble into supramolecular fibers with enhanced chirality, and the integration of conjugation provides strong aggregation tendency, leading to the formation of supramolecular fibrous bundles.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Nanoscience & Nanotechnology
Jindiao Wu, Jianan Zhang, Yanjun Liu, Jun Wang, Cheng Zhang, Jiatao Yan, Wen Li, Toshio Masuda, Andrew K. Whittaker, Afang Zhang
Summary: Molecules with C-3 symmetry and conjugated diacetylene cores can self-assemble into well-defined supramolecular fibers with enhanced chirality in both organic and aqueous solutions. The integration of symmetry and conjugation provides aggregation tendency through pi-pi stacking, resulting in supramolecular chirality predominantly influenced by steric hindrance from dipeptide pendants.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Anna A. Berseneva, Lakshani W. Masachchi, Luiz G. Jacobsohn, Hans-Conrad zur Loye
Summary: Salt-inclusion chalcogenides (SICs) are functional materials with novel topologies resulting from the combination of chalcogenide-based frameworks and salt inclusions. In this study, nine compositions of a novel family of SICs were synthesized and characterized. The stability and decomposition pathways of these SICs were predicted using density functional theory calculations. Single-crystal X-ray diffraction and energy-dispersive spectroscopy were used to investigate ion-exchange reactions, leading to the synthesis of new members of the SIC family. Photoluminescent behavior of the SIC materials was also studied, and bright orange scintillation was observed in certain samples.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Travis K. Deason, Gregory Morrison, Amir Mofrad, Hunter B. Tisdale, Jake Amoroso, David DiPrete, Gary Was, Kai Sun, Theodore M. Besmann, Hans-Conrad zur Loye
Summary: A series of quaternary Np(IV) fluorides with the compositions of NaxMNp6F30 were synthesized using a mild hydrothermal synthesis approach, where M = Ti(III), V(III), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Al(III), and Ga(III), and x = 4 for divalent metals and x = 3 for trivalent metals. The compounds have the same crystalline structure with actinide analogues NaxMAn6F30. The neptunium crystals were used to determine the ionic radii of Np(IV) (1.030(2) Å), Pu(IV) (1.014(1) Å), and Ce(IV) (1.012(2) Å). Radiation damage studies on a surrogate material indicated low resistance to amorphization. Density functional theory calculations were performed to compare the stability of the isotypic cerium and actinide structures by computing the band gaps and enthalpies of formation variations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Nanoscience & Nanotechnology
Mehran Amiri, Alice Lulich, Nan-Chieh Chiu, Samuel Wolff, Dylan B. Fast, William F. Stickle, Kyriakos C. Stylianou, May Nyman
Summary: The nuclearity of Bi nodes in coordination networks depends on solvent polarity, leading to a family of Bix-sulfonate/carboxylate coordination networks with various nuclearities. The role of the solvent is more significant than the linker in defining node topologies. Photocatalytic hydrogen generation can be achieved without a co-catalyst using certain materials from this family. The DDBS linker effectively absorbs visible light and facilitates ligand-to-Bi-node charge transfer.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
Adam A. King, Logan S. Breton, Greg Morrison, Mark D. Smith, Mingli Liang, P. Shiv Halasyamani, Hans -Conrad zur Loye
Summary: Nine new rare earth magnesium-containing thiosilicates were synthesized using the BCM method and their structures were determined. The compounds have high-quality crystals and belong to the hexagonal crystal system in the P63 space group. Magnetic measurements showed that Ce3Mg0.5SiS7, Sm3Mg0.5SiS7, and Dy3Mg0.5SiS7 exhibit paramagnetic behavior. SHG measurements of La3Mg0.5SiS7 demonstrated efficient SHG activity.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Mohammad Shohel, Jenna Bustos, Gautam D. Stroscio, Arup Sarkar, May Nyman
Summary: Technetium-99, a beta-emitter produced from (235)U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO4 (-)) with the actinides (An) during nuclear fuel reprocessing. The present study describes the synthesis and structural elucidation of a family of thorium (IV)-pertechnetate/perrhenate (ReO4 (-)) compounds, which provides comprehensive bonding information. Solution characterization shows that Th-TcO4 (-) bonding is retained in solution, whereas ReO4-Th complexes are completely dissociated.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Mohammad Usman, Matthew Christian, Mark D. Smith, Theodore Besmann, Hans -Conrad zur Loye
Summary: K0.72Fe0.72Ti1.28O4 is a layered mixed-metal oxide with the lepidocrocite structure type, grown from a molten KCl-KF mixture at 800 degrees C. The compound crystallizes in orthorhombic space group Cmcm and consists of two-dimensional layers composed of mixed Fe/Ti octahedra separated by K ions. The flux synthesis of Ni, Cu, and Zn analogs was successfully carried out based on DFT calculations, resulting in K0.77Ni0.38Ti1.62O4, K0.77Cu0.38Ti1.62O4, and K0.73Zn0.36Ti1.64O4. All four compositions can be prepared via conventional solid-state technique.
SOLID STATE SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Adrian T. Hines, Gregory Morrison, Brandon J. Yarbrough, Natalia B. Shustova, Luiz G. Jacobsohn, Hans-Conrad zur Loye
Summary: Single crystals of rare earth borates, Na3Ln(BO3)2 and K3Ln(BO3)2, were synthesized using a boric acid/hydroxide melt. Na3Ln(BO3)2 crystallized in the monoclinic system with space group P21/n, while K3Ln(BO3)2 crystallized in the orthorhombic system with space group Pnma. The luminescence of these borates under ultraviolet and X-ray excitations was investigated for the first time, and K3Tb(BO3)2 showed the highest radioluminescence intensity.
SOLID STATE SCIENCES
(2023)
Review
Chemistry, Multidisciplinary
Anna A. Berseneva, Hans-Conrad zur Loye
Summary: This article summarizes three convenient approaches for obtaining chalcogenide single crystals: solution synthesis, flux crystal growth, and single-crystal-to-single-crystal postsynthetic modifications. Chalcogenide-containing materials are important for various industries including semiconductors, thermoelectrics, superconductors, catalysis, and batteries. The synthesis of chalcogenide materials faces challenges such as the volatility of chalcogens and their reactivity with oxygen. However, various techniques have been developed for growing chalcogenide single crystals, which are useful for structure determination and property measurements.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
James A. Sommers, Jenn M. Amador, Lauren B. Fullmer, Danielle C. Hutchison, T. Wesley Surta, Oksana Ostroverkhova, May Nyman, Douglas A. Keszler
Summary: This article discusses the preparation and properties of glasses formed by aqueous solutions of zirconium and hafnium halides, as well as the crystal-glass equilibria beyond the pure glass compositions. The study reveals that the glasses are denser than their crystalline counterparts and retain specific structural units in crystals forming in contact with the glasses.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Hunter B. Tisdale, Amir M. Mofrad, Gregory Morrison, Theodore M. Besmann, Hans-Conrad zur Loye
Summary: A new series of mixed-anion alkali rare earth silicate fluorides have been synthesized via an alkali chloride/fluoride eutectic flux synthetic route. The reaction products were characterized using various techniques, and the formation enthalpies of the synthesized phases and hypothetical trivalent actinide analogues were calculated using density functional theory.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anamar Blanes-Diaz, Mohammad Shohel, Natalie T. Rice, Ida Piedmonte, Morgan A. McDonald, Kaveh Jorabchi, Stosh A. Kozimor, Jeffery A. Bertke, May Nyman, Karah E. Knope
Summary: Cerium-oxo clusters supported by acetylacetonate have been synthesized and structurally characterized in this study. The results show that these clusters can support diverse configurations in organic solutions, potentially stabilizing higher order cerium-containing clusters.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Logan S. Breton, Gregory Morrison, Hans-Conrad zur Loye
Summary: The uranium-containing 2H-perovskite-related chalcogenide family of compounds were studied using the BCM method for actinides. The synthesis and magnetic measurements of various compounds were reported, including the discovery of new compositions. A reduced radius ratio plot was presented to aid in the search for additional related sulfides.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ana Arteaga, Alice Lulich, May Nyman, Robert G. G. Surbella III
Summary: In this study, three new europium containing coordination polymers, LP-1, LP-2, and LP-3, were synthesized and characterized. LP-2 is two-dimensional, while LP-1 and LP-3 are three-dimensional. LP-1 and LP-2 exhibit modest thermal stability, while LP-3 is notably unstable and prone to degradation. Despite their apparent porosity, LP-1 and LP-2 have lower surface area and pore volumes than anticipated. Photoluminescence characterization shows bright Eu3+-based emission in all three compounds, which arises from efficient ligand-to-metal resonance energy transfer. LP-1 and LP-2 also display emission when exposed to soft X-rays, indicating potential for scintillator design.
Article
Chemistry, Inorganic & Nuclear
Gregory Morrison, Lakshani W. Masachchi, Hunter B. Tisdale, Tieyan Chang, Virginia G. Jones, K. Pilar Zamorano, Logan S. Breton, Mark D. Smith, Yu-Sheng Chen, Hans-Conrad zur Loye
Summary: Single crystals of A(3)MF(6) (A = Rb, Cs; M = Al, Ga) were grown from mixed alkali chloride/fluoride fluxes in sealed silver tubes. Multiple polymorphs were observed at room temperature for Cs3AlF6 and Cs3GaF6, while only one polymorph was observed for the Rb-containing compositions. High temperature behavior of A(3)MF(6) was studied using simultaneous TGA/DSC and high temperature SCXRD/PXRD, revealing structure transitions to the cubic structure type, c-A(3)MF(6), for all four compositions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Anna A. Berseneva, Vladislav V. Klepov, Hunter B. Tisdale, Hans-Conrad zur Loye
Summary: Two polytypic heterolayered salt-inclusion chalcogenides, o-[Na2Cl]GaQ(2) and t-[Na2Cl]GaQ(2), were synthesized via a NaCl/NaI flux-assisted method in the Na-Ga-Q (Q = S and Se) system. In the Na-Ga-Se system, the use of NaBr/NaI flux did not produce salt-inclusion phases, but resulted in the formation of Na2GaSe3 and Na4Ga2Se5 phases instead. The thermal and electronic properties of [Na2Cl]GaS2 materials were investigated, and the heterolayered [Na2Cl]GaS2 single crystals were tested as a sorbent for UO22+ uptake.
