Aluminium, gallium, indium and thallium

Kresiński, Roman A.

doi:10.1039/b508246n

Cited by 7 publications

(3 citation statements)

References 200 publications

(163 reference statements)

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“…Chemical compounds similar to (H 3 C) n X(SiH 3 ) 3−n have been studied and their properties have been reported earlier in the context of the organometallic derivative chemistry. 12,13 Complementary to our study, the (H 3 C) 3 X compounds (X = B, Al, Ga, In) are standard, commercially available, precursors for the MOCVD growth of III-nitrides. 2 Similarly to the trimethylmetal precursors, their trisilyl analogues X(SiH 3 ) 3 are also known [14][15][16][17] for X = B, Al, Ga, and In.…”

Section: Introductionmentioning

confidence: 74%

Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

et al. 2015

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We employ ab initio calculations to predict the equilibrium structure, stability, reactivity, and Raman scattering properties of sixteen different (H3C)nX(SiH3)3-n compounds (X = B, Al, Ga, In) with n = 0-3. Among this methylsilylmetal family, only the (H3C)3X members, i.e., trimethylboron (TMB), trimethylaluminum (TMA), trimethylgallium (TMG), and trimethylindium (TMI), are currently well-studied. The remaining twelve compounds proposed here open up a two-dimensional array of new possibilities for precursors in various deposition processes, and evoke potential applications in the chemical synthesis of other compounds. We infer that within the (H3C)nX(SiH3)3-n family, the compounds with fewer silyl groups (and consequently with more methyl groups) are less reactive and more stable. This trend is verified from the calculated cohesive energy, Gibbs free energy of formation, bond strength, and global chemical indices. Furthermore, we propose sequential reaction routes for the synthesis of (H3C)nX(SiH3)3-n by substitution of methyl by silyl groups, where the silicon source is the silane gas. The corresponding reaction barriers for these chemical transformations lie in the usual energy range typical for MOCVD processes. We also report the Raman spectra and light scattering properties of the newly proposed (H3C)nX(SiH3)3-n compounds, in comparison with available data of known members of this family. Thus, our computational experiment provides useful information for a systematic understanding of the stability/reactivity and for the identification of these compounds.

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Section: Introductionmentioning

confidence: 74%

Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

et al. 2015

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“…Similarly, the indium congener afforded consistent results. At this point, it is not 100% clear as to why 1b specifically acts anomalously, but given the extremely high sensitivity of the FLA method, higher coordination numbers or a different overall complex geometry for 1b in this given environment (potentially involving an agostic interaction of the Ga center with the β-H atom of the isobutyl group that is likely suppressed in 2b by the third coordinated THF molecule) could explain this discrepancy. , However, even with this deviation, the general trend confirms the effective Lewis acidity of the cationic gallium complexes in toluene as being slightly higher than that of the indium congeners (Table S2 and Figure S41).…”

Section: Results and Discussionmentioning

confidence: 99%

Rethinking the Lewis Acidity of Cationic Gallium and Indium Catalysts

Goonesinghe,

Jung,

Betinol

et al. 2023

ACS Catal.

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“…The past few decades witnessed spectacular discoveries in the chemistry of heavier main-group elements, which resemble transition metals but also possess fundamentally different electronic properties. , Materials containing indium, as a heavier main-group metal, figure prominently in the applications of gas sensors, catalysts, transparent electrodes, and nanolithography. − In particular, the investigation of crystalline indium-oxo clusters (abbreviated as InOCs), providing a platform for correlating the structure and activity at the molecular level, has recently become highly appealing. Although Wieghardt discovered the first InOCs in 1986, the number of fully characterized instances of InOCs is quite limited so far, and their corresponding applications remain almost unexplored. − In 2021, the Zhang group decoded the bixbyite-like In 12 -oxo clusters with the largest size record and explored their nanolithography application for the first time . Therefore, it is absolutely necessary to promote structural diversity and widen applications in terms of such InOCs materials.…”

Section: Introductionmentioning

confidence: 99%

Sequential Aggregation of Heterometallic {M₄X₄}-Cubanes to Wheel-Shaped In₁₀Ni₈-Oxo Clusters for Optical Limiting Application

Sun

Zhang

et al. 2023

Chem. Mater.

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It is extremely challenging but critical to regulate the structural attributes and physicochemical behaviors of metaloxo clusters in a controllable manner. Connecting versatile building units and importing aromatic ligands into crystalline materials facilitates the construction of unprecedented structures and provides a platform for the interpretation of structure−activity relationships at the molecular level. In this work, the solvent effect and organic-ligand-induced effect are exploited to formulate and regulate the variety and connection modes of cuboidal {M 4 X 4 } building units (M= In, Ni; X= O, Cl) in a controlled and incremental fashion. Not only were the inorganic basic-cubane and its dimeric analogue isolated but also their hexameric aggregation into an In 10 Ni 8 -oxo cluster with a wheel-shaped architecture was realized with the assistance of aromatic carboxylates. The In 10 Ni 8 -oxo cluster presents the largest size record in the realm of InOCs, and its peripheral surface could be modified to modulate their corresponding physicochemical properties; in particular, the benzoate and naphthoate groups can bring in abundant π•••π stacking interactions. Based on the results of Z-scan third-order nonlinear optical (NLO) measurements, these clusters present high reverse saturable absorption (RSA) suitable as optical limiting (OL) materials and constitute an instructive comparison that the general trend of the OL effect is gradually enhanced with the accumulation of more {M 4 X 4 }-cubanes including heavy atoms as well as richer and stronger π•••π stacking interactions and better delocalization. This work not only starts the research on InOCs-based optical limiting materials but also provide strategies of regulating building units for constructing heterometallic clusters.

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Aluminium, gallium, indium and thallium

Cited by 7 publications

References 200 publications

Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Rethinking the Lewis Acidity of Cationic Gallium and Indium Catalysts

Sequential Aggregation of Heterometallic {M₄X₄}-Cubanes to Wheel-Shaped In₁₀Ni₈-Oxo Clusters for Optical Limiting Application

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Aluminium, gallium, indium and thallium

Cited by 7 publications

References 200 publications

Feasibility of novel (H3C)nX(SiH3)3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Feasibility of novel (H3C)nX(SiH3)3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Rethinking the Lewis Acidity of Cationic Gallium and Indium Catalysts

Sequential Aggregation of Heterometallic {M4X4}-Cubanes to Wheel-Shaped In10Ni8-Oxo Clusters for Optical Limiting Application

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Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Sequential Aggregation of Heterometallic {M₄X₄}-Cubanes to Wheel-Shaped In₁₀Ni₈-Oxo Clusters for Optical Limiting Application