A5085021787- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Nanocluster Synthesis and Applications
- Magnetism in coordination complexes
- Metal-Organic Frameworks: Synthesis and Applications
- Metal complexes synthesis and properties
- Inorganic Chemistry and Materials
- Electrocatalysts for Energy Conversion
- Nanomaterials for catalytic reactions
- Organometallic Compounds Synthesis and Characterization
- Ferrocene Chemistry and Applications
- Pharmacological Effects and Toxicity Studies
- Advanced Nanomaterials in Catalysis
- Metalloenzymes and iron-sulfur proteins
- Crystallography and molecular interactions
- Trace Elements in Health
- Education and Critical Thinking Development
- Organometallic Complex Synthesis and Catalysis
- STEM Education
- Inorganic Fluorides and Related Compounds
- Quasicrystal Structures and Properties
- Asymmetric Hydrogenation and Catalysis
- Mathematics Education and Pedagogy
- Gold and Silver Nanoparticles Synthesis and Applications
- nanoparticles nucleation surface interactions
National Dong Hwa University
2018-2025
Hualien Tzu Chi Medical Center
2018
The first hydride-containing 2-electron palladium/copper alloys, [PdHCu11 {S2 P(Oi Pr)2 }6 (C≡CPh)4 ] (PdHCu11 ) and [PdHCu12 }5 PO(Oi Pr)} (PdHCu12 ), are synthesized from the reaction of [PdH2 Cu14 (C≡CPh)6 (PdH2 with trifluoroacetic acid (TFA). X-ray diffraction reveals that PdHCu11 PdHCu12 kernels consist a central PdH unit encapsulated within vertex-missing Cu11 cuboctahedron complete Cu12 cuboctahedron, respectively. DFT calculations indicate both can be considered as axially-distorted...
Mixed valent coinage metal clusters can encapsulate different dopants, forming remarkable superatoms while retaining a hydride. In this review, we highlight the hydride's dual nature in synthesis, structure and application of superatoms.
Abstract Atomically precise Cu‐rich bimetallic superatom clusters have been synthesized by adopting a galvanic exchange strategy. [Cu@Cu 12 (S 2 CN n Bu ) 6 (C≡CPh) 4 ][CuCl ] ( 1 was used as template to generate compositionally uniform [M@Cu ], where M=Ag ), Au 3 ). Structures of , and were determined single crystal X‐ray diffraction the results supported ESI‐MS. The anatomies – are very similar, with centred cuboctahedral cationic core that is surrounded six di‐butyldithiocarbamate (dtc)...
Cuboctahedral copper clusters containing a twelve-coordinated main group element (Cl, Br, S) at the center have been synthesized and characterized.
The structurally precise Cu-rich hydride nanoclusters [PdCu14 H2 (dtc/dtp)6 (C≡CPh)6 ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu28 H15 (S2 CNn Bu2 )12 ]+ or [Cu20 H11 {S2 P(Oi Pr)2 }9 with phenyl acetylene in presence Pd(PPh3 )2 Cl2 . Their structures and compositions determined by single-crystal X-ray diffraction results supported ESI-mass spectrometry. Hydride positions 1 confirmed neutron...
Structurally precise copper hydrides [Cu11H2{S2P(OiPr)2}6(C≡CR)3], R = Ph (1), C6H4F (2), and C6H4OMe (3), were first synthesized from the polyhydrido cluster [Cu20H11{S2P(OiPr)2}9] with nine equivalents of terminal alkynes. Later, their isolated yields significantly improved by direct synthesis [Cu(CH3CN)4](PF6), [NH4][S2P(OiPr)2], NaBH4, alkynes along NEt3 in THF. 1, 2, 3 fully characterized single-crystal X-ray diffraction, ESI-MS, multinuclear NMR spectroscopy. All three clustershave 11...
The synthesis, structural characteristics, and photophysical properties of luminescent Cu-rich bimetallic superatomic clusters [Au@Cu12(S2CNnPr2)6(C≡CPh)4]+ (1a+), [Au@Cu12{S2P(OR)2}6(C≡CPh)4]+ (2+), (2a+ = iPr; 2b+ nPr), [Au@Cu12{S2P(C2H4Ph)2}6(C≡CPh)4]+ (2c+), [Ag@Cu12{S2P(OnPr)2}6(C≡CPh)4]+ (3+) were studied. Compositionally uniform 1+–3+ isolated from the reaction dithiolato-stabilized, polyhydrido copper with phenylacetylene in presence heterometal salts. By using X-ray diffraction,...
Abstract Highly reactive copper‐dihydride clusters, [Cu 15 (H) 2 (S CNR ) 6 (C Ph) ](PF {R = n Bu ( 1 H ), Pr i 3 )}, are isolated during the reaction of 28 {S CN } 12 with ten equivalents phenylacetylene. They found to be intermediates in formation earlier reported two‐electron superatom 13 4 ] + . Better yields obtained by reacting dithiocarbamate sodium salts, [Cu(CH CN) BH − and The presence two hydrides clusters is confirmed synthesis characterization its deuteride analogue (D) , a...
In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult explore. When treated with a metal ion (Cu+ , Ag+ and Au+ ), the stable CuI dihydride template [Cu11 H2 {S2 P(Oi Pr)2 }6 (C≡CPh)3 ] (H2 Cu11 ) generates surprisingly three very different compounds, namely [CuH2 ]+ (1), [AgH2 Cu14 ((C≡CPh)6 (2), [AuCu11 Cl] (3). Compounds 1 2 both MI species maintain same number hydride ligands as their precursor. Neutron diffraction revealed first time...
Abstract A structurally precise hydride‐containing Pt‐doped Cu‐rich nanocluster [PtH 2 Cu 14 {S P(O i Pr) } 6 (CCPh) ] ( 1 ) has been synthesized. It consists of a bicapped icosahedral cage that encapsulates linear PtH unit. Upon the addition two equivalents CF 3 COOH to , hydrido clusters are isolated. These [PtHCu 11 4 ), which is vertex‐missing cuboctahedron encaging moiety, and distorted 3,3,4,4,4‐pentacapped trigonal prismatic enclosing The electronic structure analyzed by Density...
Halide ligands can serve as auxiliary for the dichalcogenolates ligands, facilitating formation of novel chalcogen-centered copper clusters. This report presents three chalcogenide-centered clusters, namely [Cu11S{S2CNnBu2}6(I)3] (1), [Cu11Se{Se2CNnPr2}6(I)3]...
Abstract A bimetallic cluster [PdHCu12{S2P(OiPr)2}6(C2Ph)3(S)] denoted as PdHCu12S was prepared by controlled exfoliation of [PdH2Cu14{S2P(OiPr)2}6(C2Ph)6] PdH2Cu14 with HTAF. Single-Crystal X-ray diffraction analysis the synthesized revealed that it has a PdH-centered cuboctahedral Cu12 core protected six dithiophosphates, sulfide, and three alkynyl ligands. The substitution C2Ph- ligand in linear H-Pd-C2Ph unit PdHCu12C sulfide altered function interstitial hydride from electron-donating...
Two structures, [Cu
The addition of two equiv. trifluoroacetic acid into the cluster templates Cu15H2 or Cu12S provokes structural change either bicapped icosahedron cuboctahedron Cu21S2 fused bi-cuboctahedron.
Abstract The structurally precise Cu‐rich hydride nanoclusters [PdCu 14 H 2 (dtc/dtp) 6 (C≡CPh) ] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate )) were synthesized from the reaction of polyhydrido copper clusters [Cu 28 15 (S CN n Bu ) 12 + or 20 11 {S P(O i Pr) } 9 with phenyl acetylene in presence Pd(PPh 3 Cl . Their structures and compositions determined by single‐crystal X‐ray diffraction results supported ESI‐mass spectrometry. Hydride positions confirmed...
A neutral polyhydrido copper cluster, [Cu27H15{S2CNnBu2}12] (abbreviated as [Cu27H15]), was prepared by the reaction of dithiocarbamates (dtc), Cu(I) salts and NaBH4. The isolated cluster provides insights into core engineering, demonstrating its novel ability to reversibly add or remove one atom from core. Single-crystal X-ray analysis reveals that new core-shell structure exhibits a Cu24 rhombicuboctahedral outer cage an inner Cu3 triangular kernel. two clusters, previously published...
Two series of hyper-coordinated halide-centered M12 cuboctahedral clusters, [M12(μ12-X){S2P(OnPr)2}6{CCPh}4](PF6), 1a-c and 2a-c (where M = Cu, 1; Ag, 2; X Cl, a; Br, b; I, c), were synthesized fully characterized by ESI-MS, multi-NMR spectroscopy, IR UV-Vis photoluminescence analysis, single-crystal X-ray crystallography. Structures 1c, 2b, 2c show a twelve-coordinated halide encapsulated in the cage, which is stabilized six dithiophosphate four alkynyl ligands. Compound 2b first Ag(I)...
Abstract In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult explore. When treated with a metal ion (Cu + , Ag and Au ), the stable Cu I dihydride template [Cu 11 H 2 {S P(O i Pr) } 6 (C≡CPh) 3 ] ( ) generates surprisingly three very different compounds, namely [CuH 1 [AgH 14 ((C≡CPh) [AuCu Cl] ). Compounds both M species maintain same number hydride ligands as their precursor. Neutron diffraction revealed first time trigonal‐pyramidal coordination mode...
Abstract The first hydride‐containing 2‐electron palladium/copper alloys, [PdHCu 11 {S 2 P(O i Pr) } 6 (C≡CPh) 4 ] ( PdHCu ) and 12 5 PO(O Pr)} ), are synthesized from the reaction of [PdH Cu 14 PdH with trifluoroacetic acid (TFA). X‐ray diffraction reveals that kernels consist a central unit encapsulated within vertex‐missing cuboctahedron complete cuboctahedron, respectively. DFT calculations indicate both can be considered as axially‐distorted superatoms. shows excellent HER activity,...
The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at level in production of clusters, including quantity dopant, characteristic ligands, charge state precursors, structural transformation, have remained a challenge. Herein, we report synthesis, purification, characterization new hydride cluster, [AuCu11(H){S2P(OiPr)2}6(C≡CPh)3]...