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Advances in Silicon Chemistry 2018
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Advances in Silicon Chemistry 2018

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 December 2018) | Viewed by 15612

Special Issue Editor

Prof. Dr. Mitsuo Kira

E-Mail Website
Guest Editor
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan
Interests: silicon chemistry; organometallic chemistry; physical organic chemistry; theoretical organometallic chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Silicon chemistry has been constantly developing as a major branch of main-group element chemistry. To see the progress and the prospect of the silicon chemistry, recently, Molecules published a Special Issue titled “Advances in Silicon Chemistry”. It successfully featured currently developing areas in basic, applied, and theoretical silicon and related heavier group-14 element chemistry. The second special issue with the same title will be launched to watch and support the progress of this important branch of chemistry. Its aim is the same as the previous issue, i.e., providing a forum for every aspect of molecular silicon and related germanium, tin and lead compounds, including their synthesis, properties, and reactions, their theoretical, spectroscopic, optoelectronic, and mechanistic studies, and their applications for materials and other applied science. The Editors strongly wish to receive many interesting and inspiring research papers on the topics.

Prof. Dr. Mitsuo Kira
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • silicon, germanium, tin, and lead compounds
  • low-coordinate and multiply-bonded compounds
  • hypercoordinate compounds
  • compounds with unusual structures
  • reactive intermediates
  • transition-metal complexes
  • theoretical studies
  • reactions and mechanisms
  • applications

Related Special Issues

Published Papers (4 papers)

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Research

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11 pages, 1355 KiB  
Communication
Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads
by Tsukasa Usuki, Kenichiro Omoto, Masaki Shimada, Yoshinori Yamanoi, Hidetaka Kasai, Eiji Nishibori and Hiroshi Nishihara
Molecules 2019, 24(3), 521; https://doi.org/10.3390/molecules24030521 - 31 Jan 2019
Cited by 12 | Viewed by 3273
Abstract
A series of disilane-linked donor‒acceptor‒donor triads (D‒Si‒Si‒A‒Si‒Si‒D) was synthesized to investigate the effects of substituents on the photophysical properties. The triads were prepared by metal-catalyzed diiodosilylation of aryl iodides using a Pd(P(t-Bu)3)2/(i-Pr)2EtN/toluene system [...] Read more.
A series of disilane-linked donor‒acceptor‒donor triads (D‒Si‒Si‒A‒Si‒Si‒D) was synthesized to investigate the effects of substituents on the photophysical properties. The triads were prepared by metal-catalyzed diiodosilylation of aryl iodides using a Pd(P(t-Bu)3)2/(i-Pr)2EtN/toluene system that we previously developed. Optical measurements, X-ray diffraction analysis, and density functional theory calculations revealed relationships between the photophysical properties and molecular structures of these triads in solution and in the solid state. The compounds emitted blue to green fluorescence in CH2Cl2 solution and in the solid state. Notably, compound 2 showed fluorescence with an absolute quantum yield of 0.17 in the solid state but showed no fluorescence in CH2Cl2. Our findings confirmed that the substituent adjacent to the disilane moiety affects the conformations and emission efficiencies of compounds in solution and in the solid state. Full article
(This article belongs to the Special Issue Advances in Silicon Chemistry 2018)
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16 pages, 2235 KiB  
Article
Spectroscopic and Structural Study of Some Oligosilanylalkyne Complexes of Cobalt, Molybdenum and Nickel
by Michaela Zirngast, Christoph Marschner and Judith Baumgartner
Molecules 2019, 24(1), 205; https://doi.org/10.3390/molecules24010205 - 08 Jan 2019
Cited by 3 | Viewed by 3339
Abstract
Metal induced stabilization of α-carbocations is well known for cobalt- and molybdenum complexed propargyl cations. The same principle also allows access to reactivity enhancement of metal coordinated halo- and hydrosilylalkynes. In a previous study, we have shown that coordination of oligosilanylalkynes to the [...] Read more.
Metal induced stabilization of α-carbocations is well known for cobalt- and molybdenum complexed propargyl cations. The same principle also allows access to reactivity enhancement of metal coordinated halo- and hydrosilylalkynes. In a previous study, we have shown that coordination of oligosilanylalkynes to the dicobalthexacarbonyl fragment induces striking reactivity to the oligosilanyl part. The current paper extends this set of oligosilanylalkyne complexes to a number of new dicobalthexacarbonyl complexes but also to 1,2-bis(cyclopentadienyl)tetracarbonyldimolybdenum and (dippe)Ni complexes. NMR-Spectroscopic and crystallographic analysis of the obtained complexes clearly show that the dimetallic cobalt and molybdenum complexes cause rehybridization of the alkyne carbon atoms to sp3, while in the nickel complexes one π-bond of the alkyne is retained. For the dicobalt and dimolybdenum complexes, strongly deshielded 29Si NMR resonances of the attached silicon atoms indicate enhanced reactivity, whereas the 29Si NMR shifts of the respective nickel complexes are similar to that of respective vinylsilanes. Full article
(This article belongs to the Special Issue Advances in Silicon Chemistry 2018)
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16 pages, 4572 KiB  
Article
Nonlinear Electrical Properties and Field Dependency of BST and Nano-ZnO-Doped Silicone Rubber Composites
by Juyi Guo, Xilin Wang, Zhidong Jia, Jun Wang and Chuan Chen
Molecules 2018, 23(12), 3153; https://doi.org/10.3390/molecules23123153 - 30 Nov 2018
Cited by 14 | Viewed by 3580
Abstract
Recently, composite materials with nonlinear dielectric or resistive properties performed well in electric field homogenization and space charge suppression in a high voltage transmission and distribution system. For the purpose of obtaining insulation materials with desirable dielectric and electrical resistance properties, we investigated [...] Read more.
Recently, composite materials with nonlinear dielectric or resistive properties performed well in electric field homogenization and space charge suppression in a high voltage transmission and distribution system. For the purpose of obtaining insulation materials with desirable dielectric and electrical resistance properties, we investigated several fillers with nonlinear electrical properties doped in silicon rubber composites, and their dependency on the temperature and field. The samples of silicone rubber composites with different components were prepared using barium strontium titanate (BST) and zinc oxide (ZnO) as the filler, and high temperature vulcanized silicone rubber (SiR) as the matrix. The investigations revealed that the BST-doped samples showed different dielectric properties compared to ZnO-doped composites, with an increase in the electric field, which was nonlinear. The resistivity of both doped samples was similar. Results demonstrated that it was possible to achieve higher values of permittivity, and lower values of tanδ and resistivity, with respect to unfilled silicone rubber composites over a wide electrical field and temperature range. Discussion of the results attributes these important functional behaviours to the spontaneous polarization of nonlinear nanoparticles and the interaction between the SiR chains and the nonlinear nanoparticles at the interfacial area. Full article
(This article belongs to the Special Issue Advances in Silicon Chemistry 2018)
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Review

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31 pages, 5765 KiB  
Review
Silicon Isotope Geochemistry: Fractionation Linked to Silicon Complexations and Its Geological Applications
by Wei Wang, Hai-Zhen Wei, Shao-Yong Jiang, Xi Liu, Fang Lei, Yi-Bo Lin and Yao Zhao
Molecules 2019, 24(7), 1415; https://doi.org/10.3390/molecules24071415 - 10 Apr 2019
Cited by 11 | Viewed by 5030
Abstract
The fundamental advances in silicon isotope geochemistry have been systematically demonstrated in this work. Firstly, the continuous modifications in analytical approaches and the silicon isotope variations in major reservoirs and geological processes have been briefly introduced. Secondly, the silicon isotope fractionation linked to [...] Read more.
The fundamental advances in silicon isotope geochemistry have been systematically demonstrated in this work. Firstly, the continuous modifications in analytical approaches and the silicon isotope variations in major reservoirs and geological processes have been briefly introduced. Secondly, the silicon isotope fractionation linked to silicon complexation/coordination and thermodynamic conditions have been extensively stressed, including silicate minerals with variable structures and chemical compositions, silica precipitation and diagenesis, chemical weathering of crustal surface silicate rocks, biological uptake, global oceanic Si cycle, etc. Finally, the relevant geological implications for meteorites and planetary core formation, ore deposits formation, hydrothermal fluids activities, and silicon cycling in hydrosphere have been summarized. Compared to the thermodynamic isotope fractionation of silicon associated with high-temperature processes, that in low-temperature geological processes is much more significant (e.g., chemical weathering, biogenic/non-biogenic precipitation, biological uptake, adsorption, etc.). The equilibrium silicon isotope fractionation during the mantle-core differentiation resulted in the observed heavy isotope composition of the bulk silicate Earth (BSE). The equilibrium fractionation of silicon isotopes among silicate minerals are sensitive to the Si–O bond length, Si coordination numbers (CN), the polymerization degrees of silicate unites, and the electronegativity of cations in minerals. The preferential enrichment of different speciation of dissoluble Si (DSi) (e.g., silicic acid H4SiO40 (H4) and H3SiO4− (H3)) in silica precipitation and diagenesis, and chemical weathering, lead to predominately positive Si isotope signatures in continental surface waters, in which the dynamic fractionation of silicon isotope could be well described by the Rayleigh fractionation model. The role of complexation in biological fractionations of silicon isotopes is more complicated, likely involving several enzymatic processes and active transport proteins. The integrated understanding greatly strengthens the potential of δ30Si proxy for reconstructing the paleo terrestrial and oceanic environments, and exploring the meteorites and planetary core formation, as well as constraining ore deposits and hydrothermal fluid activity. Full article
(This article belongs to the Special Issue Advances in Silicon Chemistry 2018)
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