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Special Issue "Advances in Materials Derived from Polyhedral Boron Clusters"

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

Deadline for manuscript submissions: 31 July 2019

Special Issue Editor

Guest Editor
Prof. Dr. Piotr Kaszyński

Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Łódź 90-363, Poland; Department of Chemistry, University of Łódź, Łódź 91-403, Poland; Organic Materials Research Group, Department of Chemistry, Middle Tennessee State University, Murfreesboro, TN 37132, USA
Website | E-Mail
Interests: carboranes; stable radicals; liquid crystals; magnetism; photophysics; photovoltaics; electro-optics; fundamental chemistry of boron clusters and radicals

Special Issue Information

Dear Colleagues,

Molecules is pleased to announce a Special Issue dedicated to materials chemistry of boron clusters. Owing their unique steric and electronic properties, polyhedral boranes are attractive structural elements for functional materials such as polymers, dendrimers, ionic liquids, liquid crystals that exhibit luminescent, nonlinear optical, electro-optical and redox properties, among the others. Interest in such specifically designed materials is rapidly increasing, as evident from recent literature reports, reviews and books.

This Special Issue of Molecules is dedicated to recent advances in synthesis, characterization and application of molecular and polymeric materials containing polyhedral boron clusters.

Prof. Dr. Piotr Kaszyński
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 papers will be 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 1800 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

  • polyhedral borane clusters
  • carboranes
  • metallaboranes
  • polymers
  • crystal engineering
  • ionic liquids
  • liquid crystals
  • photophysics including nonlinear optics
  • fundamental chemistry of materials
  • applications

Published Papers (6 papers)

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Research

Jump to: Review

Open AccessArticle Effect of Planarity of Aromatic Rings Appended to o-Carborane on Photophysical Properties: A Series of o-Carboranyl Compounds Based on 2-Phenylpyridine- and 2-(Benzo[b]thiophen-2-yl)pyridine
Molecules 2019, 24(1), 201; https://doi.org/10.3390/molecules24010201
Received: 5 December 2018 / Revised: 31 December 2018 / Accepted: 3 January 2019 / Published: 7 January 2019
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Abstract
Herein, we investigated the effect of ring planarity by fully characterizing four pyridine-based o-carboranyl compounds. o-Carborane was introduced to the C4 position of the pyridine rings of 2-phenylpyridine and 2-(benzo[b]thiophen-2-yl)pyridine (CB1 and CB2, respectively), and the compounds [...] Read more.
Herein, we investigated the effect of ring planarity by fully characterizing four pyridine-based o-carboranyl compounds. o-Carborane was introduced to the C4 position of the pyridine rings of 2-phenylpyridine and 2-(benzo[b]thiophen-2-yl)pyridine (CB1 and CB2, respectively), and the compounds were subsequently borylated to obtain the corresponding CN-chelated compounds CB1B and CB2B. Single-crystal X-ray diffraction analysis of the molecular structures of CB2 and CB2B confirmed that o-carborane is appended to the aryl moiety. In photoluminescence experiments, CB2, but not CB1, showed an intense emission, assignable to intramolecular charge transfer (ICT) transition between the aryl and o-carborane moieties, in both solution and film states. On the other hand, in both solution and film states, CB1B and CB2B demonstrated a strong emission, originating from π-π * transition in the aryl groups, that tailed off to 650 nm owing to the ICT transition. All intramolecular electronic transitions in these o-carboranyl compounds were verified by theoretical calculations. These results distinctly suggest that the planarity of the aryl groups have a decisive effect on the efficiency of the radiative decay due to the ICT transition. Full article
(This article belongs to the Special Issue Advances in Materials Derived from Polyhedral Boron Clusters)
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Open AccessArticle Synthesis and Structural Characterization of Amidine, Amide, Urea and Isocyanate Derivatives of the Amino-closo-dodecaborate Anion [B12H11NH3]
Molecules 2018, 23(12), 3137; https://doi.org/10.3390/molecules23123137
Received: 1 November 2018 / Revised: 14 November 2018 / Accepted: 16 November 2018 / Published: 29 November 2018
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Abstract
The synthesis and structural characterization of new derivatives of [B12H12]2− is of fundamental interest and is expected to allow for extended applications. Herein we report on the synthesis of a series of amidine, amide, urea and isocyanate derivatives [...] Read more.
The synthesis and structural characterization of new derivatives of [B12H12]2− is of fundamental interest and is expected to allow for extended applications. Herein we report on the synthesis of a series of amidine, amide, urea and isocyanate derivatives based on the amino-closo-dodecaborate anion [B12H11NH3]. Their structures have been confirmed by spectroscopic methods, and nine crystal structures are presented. Full article
(This article belongs to the Special Issue Advances in Materials Derived from Polyhedral Boron Clusters)
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Open AccessFeature PaperArticle Exploiting the Electronic Tuneability of Carboranes as Supports for Frustrated Lewis Pairs
Molecules 2018, 23(12), 3099; https://doi.org/10.3390/molecules23123099
Received: 13 November 2018 / Revised: 22 November 2018 / Accepted: 23 November 2018 / Published: 27 November 2018
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Abstract
The first example of a carborane with a catecholborolyl substituent, [1-Bcat-2-Ph-closo-1,2-C2B10H10] (1), has been prepared and characterized and shown to act as the Lewis acid component of an intermolecular frustrated Lewis pair in [...] Read more.
The first example of a carborane with a catecholborolyl substituent, [1-Bcat-2-Ph-closo-1,2-C2B10H10] (1), has been prepared and characterized and shown to act as the Lewis acid component of an intermolecular frustrated Lewis pair in catalyzing a Michael addition. In combination with B(C6F5)3 the C-carboranylphosphine [1-PPh2-closo-1,2-C2B10H11] (IVa) is found to be comparable with PPh2(C6F5) in its ability to catalyze hydrosilylation, whilst the more strongly basic B-carboranylphosphine [9-PPh2-closo-1,7-C2B10H11] (V) is less effective and the very weakly basic species [μ-2,2′-PPh-{1-(1′-1′,2′-closo-C2B10H10)-1,2-closo-C2B10H10}] (IX) is completely ineffective. Base strengths are rank-ordered via measurement of the 1J 31P-77Se coupling constants of the phosphineselenides [1-SePPh2-closo-1,2-C2B10H11] (2), [9-SePPh2-closo-1,7-C2B10H11] (3), and [SePPh2(C6F5)] (4). Full article
(This article belongs to the Special Issue Advances in Materials Derived from Polyhedral Boron Clusters)
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Graphical abstract

Open AccessArticle Synthesis and Ceramic Conversion of a New Organodecaborane Preceramic Polymer with High-Ceramic-Yield
Molecules 2018, 23(10), 2461; https://doi.org/10.3390/molecules23102461
Received: 25 July 2018 / Revised: 19 September 2018 / Accepted: 21 September 2018 / Published: 26 September 2018
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Abstract
Boron carbide is one of the hardest materials known, with diamond-like mechanical properties and excellent chemical stability. It is wildly used in military defense area, nuclear industry, aerospace technology, etc. Precursor-derived ceramics have made it easier to produce pure boron carbide in processed [...] Read more.
Boron carbide is one of the hardest materials known, with diamond-like mechanical properties and excellent chemical stability. It is wildly used in military defense area, nuclear industry, aerospace technology, etc. Precursor-derived ceramics have made it easier to produce pure boron carbide in processed forms and expand its applications. The challenge of this method is the synthesis of precursor polymer with high-ceramic-yield. The aim of the present work is to develop a new poly(6-norbornenyldecaborane-co-decaborane) [P(ND-co-D)] copolymer, which was successfully synthesized via ring-opening metathesis polymerization of 6-norbornenyldecaborane and tandem hydroboration with decaborane. The obtained light-yellow powder displayed good solubility, and was fully characterized by NMR, FT-IR and GPC analysis. Thermogravimetric analysis demonstrated that the char yield was up to 79%. The polymer-to-ceramic transformation process and pyrolysis mechanism has shown that the rearrangement of carbon chains of P(ND-co-D) mainly occurred in the temperature range of 350 °C~470 °C. Furthermore, the crystallization behavior and microstructures of derived ceramics were studied by XRD and SEM. Nano-sized boron carbide powders were prepared by pyrolysis of P(ND-co-D) under argon at 1400 °C for 2 h, while the structure and morphologies of the obtained rhombohedral B4C were investigated. Full article
(This article belongs to the Special Issue Advances in Materials Derived from Polyhedral Boron Clusters)
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Open AccessArticle o-Carboranylalkoxy-1,3,5-Triazine Derivatives: Synthesis, Characterization, X-ray Structural Studies, and Biological Activity
Molecules 2018, 23(9), 2194; https://doi.org/10.3390/molecules23092194
Received: 27 July 2018 / Revised: 23 August 2018 / Accepted: 29 August 2018 / Published: 30 August 2018
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Abstract
Morpholine- and bis(2-methoxyethyl)amine-substituted 1,3,5-triazine derivatives containing an alkoxy-o-carborane in the 6-position of the triazine ring were successfully synthesized. The molecular structures of the methoxy- and ethoxy-o-carboranyl-1,3,5-triazines were established by X-ray crystallography. In vitro studies showed that the methylene bridged morpholine- and bis(2-methoxyethyl)amine-substituted o-carboranyl-1,3,5-triazines [...] Read more.
Morpholine- and bis(2-methoxyethyl)amine-substituted 1,3,5-triazine derivatives containing an alkoxy-o-carborane in the 6-position of the triazine ring were successfully synthesized. The molecular structures of the methoxy- and ethoxy-o-carboranyl-1,3,5-triazines were established by X-ray crystallography. In vitro studies showed that the methylene bridged morpholine- and bis(2-methoxyethyl)amine-substituted o-carboranyl-1,3,5-triazines accumulated to high levels in B16 melanoma cells and exhibited higher cytotoxicity than p-boronophenylalanine. Full article
(This article belongs to the Special Issue Advances in Materials Derived from Polyhedral Boron Clusters)
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Review

Jump to: Research

Open AccessFeature PaperReview Ferrocene and Transition Metal Bis(Dicarbollides) as Platform for Design of Rotatory Molecular Switches
Molecules 2017, 22(12), 2201; https://doi.org/10.3390/molecules22122201
Received: 2 November 2017 / Revised: 27 November 2017 / Accepted: 1 December 2017 / Published: 11 December 2017
Cited by 3 | PDF Full-text (13382 KB) | HTML Full-text | XML Full-text
Abstract
Design of rotatory molecular switches based on extremely stable sandwich organometallic complexes ferrocene and bis(dicarbollide) complexes of transition metals is reviewed. The “on”–“off” switching in these systems can be controlled by various external stimuli such as change of the solution pH, interactions with [...] Read more.
Design of rotatory molecular switches based on extremely stable sandwich organometallic complexes ferrocene and bis(dicarbollide) complexes of transition metals is reviewed. The “on”–“off” switching in these systems can be controlled by various external stimuli such as change of the solution pH, interactions with coordinating species or redox reactions involving the central atom or substituents in the ligands. Full article
(This article belongs to the Special Issue Advances in Materials Derived from Polyhedral Boron Clusters)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Author: Hye Jin Bae 1, Kang Mun Lee 2, Myung Hwan Park 3
Affiliation:
1. Samsung Advanced Institute of Technology, Suwon, Gyeoggi 16678, Republic of Korea.
2.Department of Chemistry, Kangwon National University, Chuncheon, Gangwon 24341, Republic of Korea.
3.Department of Chemistry Education, Chungbuk National University, Cheongju, Chungbuk 28644, Republic of Korea.
Tentative title: Intriguing Photophysical Properties of N,C-Chelate Four-Coordinated Organoboron Complexes Possesing o-Carborane Cages
Abstract: Four-coordinate organoboron compounds have attracted great attention due to their potential application in organic light-emitting diodes (OLEDs), sensory and photo-responsive materials. In an effort to design a novel moiety of four-coordinate organoboron compounds, we have been interested in 1,2-closo-C2B10H12, so called o-carborane as a substituent since it possesses the unique photophysical properties such as a highly polarizable σ-aromatic achracter, electron-deficient nature, and good thermal and electrochemical stability. Consequently, we introduced the o-carborane cages to the 4- or 5-position of the pyridine ring of the btp (2,6-bis(1,2,3-triazol-4-yl)pyridine) and ppy (2-phenylpyridine) ligands which are the ligand for four-coordinate organoboron compounds. These complexes were synthesized in moderated yield and investigated the photophysical, thermal, and electrochemical characters

Author: Alan J. Welch
Institute of Chemical Sciences, School of Engineering & Physical Sciences, Heriot-Watt University,UK
Tentative Title: Exploiting the Electronic Tuneability of Carboranes as Supports for Frustrated Lewis Pairs
Tentative abstract: It is well-known that carboranes can function as either electron-donating or electron-releasing units depending on whether they are substituted at boron or carbon, respectively. Thus carborane supports can be used modify the strength of Lewis acids and/or Lewis bases which are appended to them. This has the potential to be of great value in Frustrated Lewis Pair (FLP) chemistry since the ability of an FLP to catalyse a particular reaction is critically dependent on the acid and/or base strength.
In this paper we report the first examples of both acid and base FLP components bound to carborane supports and their applications in catalysis. We also report synthetic and spectroscopic studies of derivatives of the Lewis base components which allow us to rank order their Lewis base strengths. The rank order thus established agrees well with the relative catalytic performance of the Lewis base components.

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