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New Boron Chemistry: Current Advances and Future Prospects

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

Deadline for manuscript submissions: closed (31 May 2023) | Viewed by 16754

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Dr. Felipe Fantuzzi

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Guest Editor

School of Physical Sciences, University of Kent, Canterbury CT2 7NZ, UK
Interests: main-group chemistry; chemical bonding; computational chemistry; theoretical chemistry; materials chemistry

Prof. Dr. Marco A. C. Nascimento

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Guest Editor

Chemistry Institute, Federal University of Rio de Janeiro, Rio de Janeiro 21941-909, Brazil
Interests: main-group chemistry; nanostructured materials; flame-retardant materials; materials for CO₂ capture and conversion; heterogeneous catalysis; atomic and molecular spectroscopy; nature of the chemical bond; computational chemistry

Special Issue Information

Dear Colleagues,

Boron, an important member of the main-group elements, plays an important role in modern chemistry and human life. Boron and its compounds are widely used in inorganic, organic and organometallic, and medicinal chemistry. Meanwhile, these systems have also stepped onto the stage of the materials industry from the role of basic science materials due to their unique and fascinating physico-chemical properties. The combination of state-of-the-art experimental and computational methods is contributing not only to a deep understanding of fundamental aspects in boron chemistry, but also paving the way for novel potential applications in distinct research fields and industries.

This Special Issue, “New Boron Chemistry: Current Advances and Future Prospects”, aims to focus on cutting-edge research related to boron chemistry. Specific topics include, but are not limited to, the development of novel synthetic methodologies, bonding analysis of boron compounds, cluster boron chemistry, structural elucidations, bonding analysis, as well as possible applications in all fields of boron chemistry. Manuscripts addressing other relevant and challenging problems are also strongly encouraged.

We cordially invite researchers working in this field to contribute original research articles, short communications, and critical review articles. Short papers on one compound will also be welcome in this Special Issue of Molecules.

Dr. Felipe Fantuzzi
Prof. Dr. Marco A. C. Nascimento
Guest Editors

Manuscript Submission Information

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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.

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Keywords

boron chemistry
boranes and diboranes
metal–boron complexes
borylenes
diborenes and di-borynes
boron-based aromatics
boron materials
boron catalysis
bonding analysis of boron compounds
cluster boron chemistry
boron in synthesis and organic chemistry
computational boron chemistry

Published Papers (10 papers)

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Research

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15 pages, 4510 KiB

Open AccessArticle

Chemistry of CS₂ and CS₃ Bridged Decaborane Analogues: Regular Coordination Versus Cluster Expansion

by Ketaki Kar, Suvam Saha, Rahul Maganbhai Parmar, Arindam Roy, Marie Cordier, Thierry Roisnel and Sundargopal Ghosh

Molecules 2023, 28(3), 998; https://doi.org/10.3390/molecules28030998 - 19 Jan 2023

Viewed by 1519

Abstract

In an effort to synthesize metallaheteroborane clusters of higher nuclearity, the reactivity of metallaheteroboranes, nido-[(Cp*M)₂B₆S₂H₄(CS₃)] (Cp* = C₅Me₅) (1: M = Co; 2: M = Rh) with various metal carbonyls have been investigated. Photolysis of nido-1 and nido-2 with group 6 metal carbonyls, M’(CO)₅.THF (M’ = Mo or W) were performed that led to the formation of a series of adducts [(Cp*M)₂B₆S₂H₄(CS₃){M’(CO)₅}] (3: M = Co, M’ = Mo; 4: M = Co, M’ = W; 5: M = Rh, M’ = Mo; 6: M = Rh, M’ = W) instead of cluster expansion reactions. In these adducts, the S atom of C=S group of di(thioboralane)thione {B₂CS₃} moiety is coordinated to M’(CO)₅ (M = Mo or W) in η¹-fashion. On the other hand, thermolysis of nido-1 with Ru₃(CO)₁₂ yielded one fused metallaheteroborane cluster [{Ru(CO)₃}₃S{Ru(CO)}{Ru(CO)₂}Co₂B₆SH₄(CH₂S₂){Ru(CO)₃}₂S], 7. This 20-vertex-fused cluster is composed of two tetrahedral {Ru₃S} and {Ru₂B₂}, a flat butterfly {Ru₃S} and one octadecahedron {Co₂RuB₇S} core with one missing vertex, coordinated to {Ru₂SCH₂S₂} through two boron and one ruthenium atom. On the other hand, the room temperature reaction of nido-2 with Co₂(CO)₈ produced one 19-vertex fused metallaheteroborane cluster [(Cp*Rh)₂B₆H₄S₄{Co(CO)}₂{Co(CO)₂}₂(μ-CO)S{Co(CO)₃}₂], 8. Cluster 8 contains one nido-decaborane {Rh₂B₆S₂}, one butterfly {Co₂S₂} and one bicapped square pyramidal {Co₆S} unit that exhibits an intercluster fusion with two sulfur atoms in common. Clusters 3–6 have been characterized by multinuclear NMR and IR spectroscopy, mass spectrometry and structurally determined by XRD analyses. Furthermore, the DFT calculations have been carried out to gain insight into electronic, structural and bonding patterns of the synthesized clusters. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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11 pages, 2053 KiB

Open AccessArticle

F₂BMF (M = B and Al) Molecules: A Matrix Infrared Spectra and Theoretical Calculations Investigation

by Juanjuan Cheng, Liyan Cai, Zhen Pu, Bing Xu and Xuefeng Wang

Molecules 2023, 28(2), 554; https://doi.org/10.3390/molecules28020554 - 05 Jan 2023

Viewed by 1062

Abstract

Reactions of laser-ablated B and Al atoms with BF₃ have been explored in the 4 K excess neon through the matrix isolation infrared spectrum, isotopic substitutions and quantum chemical calculations. The inserted complexes F₂BMF (M = B, Al) were identified by anti-symmetric and symmetric stretching modes of F-B-F, and the F-¹¹B-F stretch modes are at 1336.9 and 1202.4 cm⁻¹ for F₂¹¹B¹¹BF and at 1281.5 and 1180.8 cm⁻¹ for F₂¹¹BAlF. The CASSCF analysis, EDA-NOCV calculation and the theory of atoms-in-molecules (AIM) are applied to investigate the bonding characters of F₂BBF and F₂BAlF molecules. The bonding difference between boron and aluminum complexes reveals interesting chemistries, and the FB species stabilization by a main group atom was first observed in this article. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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13 pages, 2536 KiB

Open AccessArticle

Structural Evolution and Electronic Properties of Selenium-Doped Boron Clusters SeB_n^0/− (n = 3–16)

by Yue-Ju Yang, Shi-Xiong Li, De-Liang Chen and Zheng-Wen Long

Molecules 2023, 28(1), 357; https://doi.org/10.3390/molecules28010357 - 01 Jan 2023

Cited by 5 | Viewed by 1478

Abstract

A theoretical research of structural evolution, electronic properties, and photoelectron spectra of selenium-doped boron clusters SeB_n^0/− (n = 3–16) is performed using particle swarm optimization (CALYPSO) software in combination with density functional theory calculations. The lowest energy structures of SeB_n^0/− (n = 3–16) clusters tend to form quasi-planar or planar structures. Some selenium-doped boron clusters keep a skeleton of the corresponding pure boron clusters; however, the addition of a Se atom modified and improved some of the pure boron cluster structures. In particular, the Se atoms of SeB₇⁻, SeB₈⁻, SeB₁₀⁻, and SeB₁₂⁻ are connected to the pure quasi-planar B₇⁻, B₈⁻, B₁₀⁻, and B₁₂⁻ clusters, which leads to planar SeB₇⁻, SeB₈⁻, SeB₁₀⁻, and SeB₁₂⁻, respectively. Interestingly, the lowest energy structure of SeB₉⁻ is a three-dimensional mushroom-shaped structure, and the SeB₉⁻ cluster displays the largest HOMO–LUMO gap of 5.08 eV, which shows the superior chemical stability. Adaptive natural density partitioning (AdNDP) bonding analysis reveals that SeB₈ is doubly aromatic, with 6 delocalized π electrons and 6 delocalized σ electrons, whereas SeB₉⁻ is doubly antiaromatic, with 4 delocalized π electrons and 12 delocalized σ electrons. Similarly, quasi-planar SeB₁₂ is doubly aromatic, with 6 delocalized π electrons and 14 delocalized σ electrons. The electron localization function (ELF) analysis shows that SeB_n^0/− (n = 3–16) clusters have different local electron delocalization and whole electron delocalization effects. The simulated photoelectron spectra of SeB_n⁻ (n = 3–16) have different characteristic bands that can identify and confirm SeB_n⁻ (n = 3–16) combined with future experimental photoelectron spectra. Our research enriches the geometrical structures of small doped boron clusters and can offer insight for boron-based nanomaterials. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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12 pages, 2751 KiB

Open AccessArticle

Planar Elongated B₁₂ Structure in M₃B₁₂ Clusters (M = Cu-Au)

by José Solar-Encinas, Alejandro Vásquez-Espinal, Luis Leyva-Parra, Osvaldo Yañez, Diego Inostroza, Maria Luisa Valenzuela, Walter Orellana and William Tiznado

Molecules 2023, 28(1), 236; https://doi.org/10.3390/molecules28010236 - 28 Dec 2022

Viewed by 1521

Abstract

Here, it is shown that the M₃B₁₂ (M = Cu-Au) clusters’ global minima consist of an elongated planar B₁₂ fragment connected by an in-plane linear M₃ fragment. This result is striking since this B₁₂ planar structure is not favored in the bare cluster, nor when one or two metals are added. The minimum energy structures were revealed by screening the potential energy surface using genetic algorithms and density functional theory calculations. Chemical bonding analysis shows that the strong electrostatic interactions with the metal compensate for the high energy spent in the M₃ and B₁₂ fragment distortion. Furthermore, metals participate in the delocalized π-bonds, which infers an aromatic character to these species. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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12 pages, 2366 KiB

Open AccessArticle

Can the Fluxionality in Borospherene Influence the Confinement-Induced Bonding between Two Noble Gas Atoms?

by Ranita Pal and Pratim Kumar Chattaraj

Molecules 2022, 27(24), 8683; https://doi.org/10.3390/molecules27248683 - 08 Dec 2022

Cited by 2 | Viewed by 909

Abstract

A density functional theory study is performed to determine the stability and bonding in the neon dimer inside the B₃₀N₃₀ fullerene cage, the fluxional B₄₀ cage, and within non-fluxional cages such as B₁₂N₁₂ and C₆₀. The nature of bonding in the Ne₂ encapsulated B₄₀ is compared with the that in other cages in an attempt to determine whether any possible alterations are brought about by the dynamical nature of the host cage apart from the associated confinement effects. The bonding analysis includes the natural bond order (NBO), Bader’s Atoms-in-Molecules electron density analysis (AIM), and energy decomposition analysis (EDA), revealing the non-covalent nature of the interactions between the Ne atoms and that between the Ne and the cage atoms. The formation of all the Ne₂@cage systems is thermochemically unfavourable, the least being that for the B₃₀N₃₀ cage, which can easily be made favourable at lower temperatures. The Ne-Ne distance is lowest in the smallest cage and increases as the cage size increase due to steric relaxation experienced by the dimer. The dynamical picture of the systems is investigated by performing ab initio molecular dynamics simulations using the atom-centred density matrix propagation (ADMP) technique, which shows the nature of the movement of the dimer inside the cages, and by the fact that since it moves as a single entity, a weak bonding force holds them together, apart from their proven kinetic stability. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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12 pages, 3567 KiB

Open AccessArticle

Theoretical Study of Hydrogen Production from Ammonia Borane Catalyzed by Metal and Non-Metal Diatom-Doped Cobalt Phosphide

by Dong-Heng Li, Qiao-Mei Li, Shuang-Ling Qi, Hai-Chuan Qin, Xiao-Qin Liang and Laicai Li

Molecules 2022, 27(23), 8206; https://doi.org/10.3390/molecules27238206 - 24 Nov 2022

Cited by 6 | Viewed by 1365

Abstract

The decomposition of ammonia borane (NH₃BH₃) to produce hydrogen has developed a promising technology to alleviate the energy crisis. In this paper, metal and non-metal diatom-doped CoP as catalyst was applied to study hydrogen evolution from NH₃BH₃ by density functional theory (DFT) calculations. Herein, five catalysts were investigated in detail: pristine CoP, Ni- and N-doped CoP (CoP_Ni-N), Ga- and N-doped CoP (CoP_Ga-N), Ni- and S-doped CoP (CoP_Ni-S), and Zn- and S-doped CoP (CoP_Zn-S). Firstly, the stable adsorption structure and adsorption energy of NH₃BH₃ on each catalytic slab were obtained. Additionally, the charge density differences (CDD) between NH₃BH₃ and the five different catalysts were calculated, which revealed the interaction between the NH₃BH₃ and the catalytic slab. Then, four different reaction pathways were designed for the five catalysts to discuss the catalytic mechanism of hydrogen evolution. By calculating the activation energies of the control steps of the four reaction pathways, the optimal reaction pathways of each catalyst were found. For the five catalysts, the optimal reaction pathways and activation energies are different from each other. Compared with undoped CoP, it can be seen that CoP_Ga-N, CoP_Ni-S, and CoP_Zn-S can better contribute hydrogen evolution from NH₃BH₃. Finally, the band structures and density of states of the five catalysts were obtained, which manifests that CoP_Ga-N, CoP_Ni-S, and CoP_Zn-S have high-achieving catalytic activity and further verifies our conclusions. These results can provide theoretical references for the future study of highly active CoP catalytic materials. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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7 pages, 13345 KiB

Open AccessArticle

B₃Al₄⁺: A Three-Dimensional Molecular Reuleaux Triangle

by Li-Xia Bai, Mesías Orozco-Ic, Ximena Zarate, Dage Sundholm, Sudip Pan, Jin-Chang Guo and Gabriel Merino

Molecules 2022, 27(21), 7407; https://doi.org/10.3390/molecules27217407 - 01 Nov 2022

Cited by 4 | Viewed by 2722

Abstract

We systematically explore the potential energy surface of the B₃Al₄⁺ combination of atoms. The putative global minimum corresponds to a structure formed by an Al₄ square facing a B₃ triangle. Interestingly, the dynamical behavior can be described as a Reuleaux molecular triangle since it involves the rotation of the B₃ triangle at the top of the Al₄ square. The molecular dynamics simulations, corroborating with the very small rotational barriers of the B₃ triangle, show its nearly free rotation on the Al₄ ring, confirming the fluxional character of the cluster. Moreover, while the chemical bonding analysis suggests that the multicenter interaction between the two fragments determines its fluxionality, the magnetic response analysis reveals this cluster as a true and fully three-dimensional aromatic system. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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14 pages, 1929 KiB

Open AccessArticle

Relationship between the Molecular Geometry and the Radiative Efficiency in Naphthyl-Based Bis-Ortho-Carboranyl Luminophores

by Sanghee Yi, Mingi Kim, Chan Hee Ryu, Dong Kyun You, Yung Ju Seo and Kang Mun Lee

Molecules 2022, 27(19), 6565; https://doi.org/10.3390/molecules27196565 - 04 Oct 2022

Cited by 3 | Viewed by 1518

Abstract

The efficiency of intramolecular charge transfer (ICT)-based emission on π-aromatic-group-appended closo-ortho-carboranyl luminophores is known to be affected by structural fluctuations and molecular geometry, but investigation of this relationship has been in progress to date. In this study, four naphthyl-based bis-o-carboranyl compounds, in which hydrogen (15CH and 26CH) or trimethysilyl groups (15CS and 26CS) were appended at the o-carborane cage, were synthesized and fully characterized. All the compounds barely displayed an emissive trace in solution at 298 K; however, 15CH and 26CH distinctly exhibited a dual emissive pattern in rigid states (in solution at 77 K and in films), attributed to locally excited (LE) and ICT-based emission, while 15CS and 26CS showed strong ICT-based greenish emission. Intriguingly, the molecular structures of the four compounds, analyzed by single X-ray crystallography, showed that the C-C bond axis of the o-carborane cage in the trimethysilyl group-appended compounds 15CS and 26CS were more orthogonal to the plane of the appended naphthyl group than those in 15CH and 26CH. These features indicate that 15CS and 26CS present an efficient ICT transition based on strong exo-π-interaction, resulting in a higher quantum efficiency (Φ_em) for ICT-based radiative decay than those of 15CH and 26CH. Moreover, the 26CS structure revealed most orthogonal geometry, resulting in the highest Φ_em and lowest k_nr values for the ICT-based emission. Consequently, all the findings verified that efficient ICT-based radiative decay of aromatic group-appended o-carboranyl luminophores could be achieved by the formation of a specific geometry between the o-carborane cage and the aromatic plane. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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17 pages, 4236 KiB

Open AccessArticle

Synthesis and Strong Solvatochromism of Push-Pull Thienylthiazole Boron Complexes

by Martijn J. Wildervanck, Reinhard Hecht and Agnieszka Nowak-Król

Molecules 2022, 27(17), 5510; https://doi.org/10.3390/molecules27175510 - 27 Aug 2022

Cited by 4 | Viewed by 1711

Abstract

The solvatochromic behavior of two donor-π bridge-acceptor (D-π-A) compounds based on the 2-(3-boryl-2-thienyl)thiazole π-linker and indandione acceptor moiety are investigated. DFT/TD-DFT calculations were performed in combination with steady-state absorption and emission measurements, along with electrochemical studies, to elucidate the effect of two different strongly electron-donating hydrazonyl units on the solvatochromic and fluorescence behavior of these compounds. The Lippert–Mataga equation was used to estimate the change in dipole moments (Δµ) between ground and excited states based on the measured spectroscopic properties in solvents of varying polarity with the data being supported by theoretical studies. The two asymmetrical D-π-A molecules feature strong solvatochromic shifts in fluorescence of up to ~4300 cm⁻¹ and a concomitant change of the emission color from yellow to red. These changes were accompanied by an increase in Stokes shift to reach values as large as ~5700–5800 cm⁻¹. Quantum yields of ca. 0.75 could be observed for the N,N-dimethylhydrazonyl derivative in nonpolar solvents, which gradually decreased along with increasing solvent polarity, as opposed to the consistently reduced values obtained for the N,N-diphenylhydrazonyl derivative of up to ca. 0.20 in nonpolar solvents. These two push–pull molecules are contrasted with a structurally similar acceptor-π bridge-acceptor (A-π-A) compound. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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Review

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42 pages, 16363 KiB

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Tris(pentafluorophenyl)borane-catalyzed Hydride Transfer Reactions in Polysiloxane Chemistry—Piers–Rubinsztajn Reaction and Related Processes

by Slawomir Rubinsztajn, Julian Chojnowski and Urszula Mizerska

Molecules 2023, 28(16), 5941; https://doi.org/10.3390/molecules28165941 - 08 Aug 2023

Cited by 2 | Viewed by 1811

Abstract

Tris(pentafluorophenyl)borane (TPFPB) is a unique Lewis acid that catalyzes the condensation between hydrosilanes (Si-H) and alkoxysilanes (Si-OR), leading to the formation of siloxane bonds (Si-OSi) with the release of hydrocarbon (R-H) as a byproduct—the so-called Piers–Rubinsztajn reaction. The analogous reactions of hydrosilanes with silanols (Si-OH), alcohols (R-OH), ethers (R-OR′) or water in the presence of TPFPB leads to the formation of a siloxane bond, alkoxysilane (Si-OR or Si-OR′) or silanol (Si-OH), respectively. The above processes, often referred to as Piers–Rubinsztajn reactions, provide new synthetic tools for the controlled synthesis of siloxane materials under mild conditions with high yields. The common feature of these reactions is the TPFPB-mediated hydride transfer from silicon to carbon or hydrogen. This review presents a summary of 20 years of research efforts related to this field, with a focus on new synthetic methodologies leading to numerous previously difficult to synthesize well-defined siloxane oligomers, polymers and copolymers of a complex structure and potential applications of these new materials. In addition, the mechanistic aspects of the recently discovered reactions involving hydride transfer from silicon to silicon are discussed in more detail. Full article

(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)

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