Polymorphism of Au11(PR3)7Cl3 clusters: understanding C–H⋯π interaction and C–H⋯Cl–C van der Waals interaction on cluster assembly by surface modification

Qin, Chenwanli; Yuan, Qianqin; Wang, Shuxin; Chen, Shuang; Zhu, Manzhou

doi:10.1039/d0ra01288b

Cited by 6 publications

(3 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[12][13][14] Previous reports have mentioned that the Au 12 (SCH 3 ) + 9 cluster exhibits a catalytic role in some environmental conditions. [15][16][17][18][19][20][21][22][23][24][25][26] Chen et al [27] experimentally constructed a graphene oxide nanostructure decorated with Ag nanoparticles, which demonstrated the high sensitivity to NH 3 . Theoretical studies about the adsorption of Pt 13 [28] and Fe 13 (or Al 13 ) [29] nanoclusters on graphene have been reported.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of M ₆ X ₂ and M ₆ XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Li¹,

Cheng²,

Zhang³

2022

Chinese Phys. B

View full text Add to dashboard Cite

MoS2, a transition metal dichalcogenide (TMDC), has attracted a significant amount of attention due to its direct bandgap, tunability and optical properties. Recently, a novel structure consisting of MoS2 and noble metal nanoclusters has been reported. Inspired by this, first-principles calculations were implemented to predict the structures of M6X2 and M6XX' (M = Au, Ag; X, X' = S, Se). The calculated bandgap, band edge position, and optical absorption of these structures prove that the silver compounds (Ag6X2 and Ag6XX') have great potential for catalytic water splitting. In addition, biaxial strain (tensile strain and compressive strain) was applied to adjust the properties of these materials. The bandgap presents a quasi-linear trend with increasing applied strain intensity. Moreover, the transition between the direct and indirect bandgap was found. The outstanding electronic and optical properties of these materials provide strong evidence for the application in microelectronic devices, photoelectric devices, and photocatalytic materials.

show abstract

Section: Introductionmentioning

confidence: 99%

Theoretical study of M ₆ X ₂ and M ₆ XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Li¹,

Cheng²,

Zhang³

2022

Chinese Phys. B

View full text Add to dashboard Cite

show abstract

“…These noncovalent interactions contribute to the structural stability of the nanocluster. 27 Optical band gap decreases in solid-state samples compared to liquid state (Supporting Information, Figures S3 and S4) by 0.32 eV, possibly due to the C−H----I and π-stacking interactions splitting the states in band structure and reducing the gap. 28 The electrochemical band gap was found to be 1.1 eV (Supporting Information, Figure S5).…”

Section: Resultsmentioning

confidence: 99%

“…The phenyl rings of the phosphine ligand on adjacent clusters also interact through π-clouds and these rings are separated by a distance ∼3.78 Å. These noncovalent interactions contribute to the structural stability of the nanocluster . Optical band gap decreases in solid-state samples compared to liquid state (Supporting Information, Figures S3 and S4) by 0.32 eV, possibly due to the C–H----I and π-stacking interactions splitting the states in band structure and reducing the gap .…”

Section: Resultsmentioning

confidence: 99%

Defects Engineering on Ceria and C–C Coupling Reactions Using [Au₁₁(PPh₃)₇I₃] Nanocluster: A Combined Experimental and Theoretical Study

et al. 2020

View full text Add to dashboard Cite

Ligand protected atom-precise gold-based catalysts have been utilized in many essential chemical processes, but their mechanism and the fate of the catalyst during reaction are still unrevealed. Atom-precise cluster without ligands are thus highly desirable to maximize atom efficiency, but making these in solution phase is challenging. In this scenario, catalysts with dispersion on oxide support are highly desirable to understand the role of metal core during catalytic reaction. Here, we report the synthesis of Au11(PPh3)7I3 cluster that consists of an incomplete icosahedron core. During its impregnation process on CeO2 support, all of the ligands were removed from the kernel and the Au11 kernel fits into the defects of ceria (embedded onto the oxygen vacancy of ceria (111) plane). This Au11@CeO2 has high atom efficiency and catalytic activity for Ullmann-type C–C homocoupling reactions for electron rich substrates. Density functional theory calculations showed that hexagonal arrangements of Au11 kernel on (111) plane of CeO2 is the most stable one. Theoretical calculations also proved that the atop gold atom has more favorable interaction with phenyl iodide than the second layer gold atoms of the Au11@CeO2. This demonstrated that the present catalyst mimics the single-atom catalyst-like behavior in facilitating the coupling reactions.

show abstract

Polymorphism and White Light Emission of 1‐Bromo‐3,5,7‐triphenyladamantane Compared with 1,3,5,7‐Tetraphenyladamantane

Gowrisankar,

Fokin,

Becker

et al. 2024

Eur J Org Chem

View full text Add to dashboard Cite

Here we report our investigation of 1‐bromo‐3,5,7‐triphenyladamantane (1) and the elucidation of polymorphic crystals (1A and 1B) using single crystal X‐ray diffraction. In the monoclinic crystal system of 1A (P21/n), we observed CH−π interactions, while Br···Br interactions are absent. Conversely, the Br···Br interactions are an apparent factor in the formation of the monoclinic crystal system of 1B (R3). We compare our findings with 1,3,5,7‐tetraphenyladamantane (2), characterized by numerous CH−π interactions in the solid. Computational analyses were employed to investigate the interactions within the characteristic dimers present in the unit cells of 1A and 1B, including visualization of noncovalent interactions and the use of the atoms‐in‐molecules approach, and MO analysis. These support the notion of London dispersion (LD) dimer‐dimer interactions in 1A between the phenyl moieties, whereas 1B exhibits additional dimer‐dimer Br···Br contacts. In contrast, the crystals of 2 are exclusively held together by CH−π stacking LD interactions, a feature absent in the polymorphs of 1. Both polymorphic forms of 1 emit white light when subjected to 900 nm continuous wave laser irradiation, displaying a subtle blue shift compared to 2. The absence of CH−π stacking interactions between the dimers of 1 causes a small red‐shift in the emission spectrum.

show abstract

Polymorphism of Au₁₁(PR₃)₇Cl₃ clusters: understanding C–H⋯π interaction and C–H⋯Cl–C van der Waals interaction on cluster assembly by surface modification

Abstract: C–H⋯π interactions and C–H⋯Cl–C van der Waals interactions are dominant in the crystallization of Au11(PR3)7Cl3 clusters, resulting in a crystal system transformation.

Cited by 6 publications

References 41 publications

Theoretical study of M ₆ X ₂ and M ₆ XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Theoretical study of M ₆ X ₂ and M ₆ XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Defects Engineering on Ceria and C–C Coupling Reactions Using [Au₁₁(PPh₃)₇I₃] Nanocluster: A Combined Experimental and Theoretical Study

Polymorphism and White Light Emission of 1‐Bromo‐3,5,7‐triphenyladamantane Compared with 1,3,5,7‐Tetraphenyladamantane

Contact Info

Product

Resources

About

Polymorphism of Au11(PR3)7Cl3 clusters: understanding C–H⋯π interaction and C–H⋯Cl–C van der Waals interaction on cluster assembly by surface modification

Abstract: C–H⋯π interactions and C–H⋯Cl–C van der Waals interactions are dominant in the crystallization of Au11(PR3)7Cl3 clusters, resulting in a crystal system transformation.

Cited by 6 publications

References 41 publications

Theoretical study of M 6 X 2 and M 6 XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Theoretical study of M 6 X 2 and M 6 XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Defects Engineering on Ceria and C–C Coupling Reactions Using [Au11(PPh3)7I3] Nanocluster: A Combined Experimental and Theoretical Study

Polymorphism and White Light Emission of 1‐Bromo‐3,5,7‐triphenyladamantane Compared with 1,3,5,7‐Tetraphenyladamantane

Contact Info

Product

Resources

About

Polymorphism of Au₁₁(PR₃)₇Cl₃ clusters: understanding C–H⋯π interaction and C–H⋯Cl–C van der Waals interaction on cluster assembly by surface modification

Theoretical study of M ₆ X ₂ and M ₆ XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Theoretical study of M ₆ X ₂ and M ₆ XX′ structure (M = Au, Ag; X,X′ = S, Se): Electronic and optical properties, ability of photocatalytic water splitting, and tunable properties under biaxial strain

Defects Engineering on Ceria and C–C Coupling Reactions Using [Au₁₁(PPh₃)₇I₃] Nanocluster: A Combined Experimental and Theoretical Study