Cyclic (Alkyl)(Amino)Carbene-Iminoboryl Compounds with Three Formal Oxidation States.

BN/CC isosterism is an effective strategy to build hybrid functional molecules with unique properties. In contrast to the alkynyl iminium salts derived from cyclic (alkyl)(amino)carbenes (CAACs) that feature only one reversible reduction wave, the isoelectronic cationic CAAC-iminoboryl adducts could be singly and doubly reduced smoothly. Both the resultant neutral radical and anionic azaborataallenes bear NBC-mixed allenic structures. The former radical has a high spin-density of 0.55e at CCAAC carbon, yet exhibits formal boron-centered radical reactivity. The latter azaborataallenes feature the nucleophilic CCAAC center and polar N(δ-)═B(δ+)═C(δ-) unit, and readily undergo nucleophilic substitution, isocyanide insertion, dipolar addition and cycloaddition reactions etc. The N-substituents have been shown to have a significant influence on the solid-state structure, thermal stability, and reactivity of azaborataallenes. This work showcases the allenic BN-unsaturated species as versatile building blocks in organic synthesis.

Aromatic 1,4,2,3-Diazadiborole Featuring an Unsymmetrical B=B Entity: A Versatile Synthon for Unusual Boron Heterocycles.

The replacement of a CC unit with an isoelectronic BN unit in aromatic systems can give rise to molecules and materials with fascinating properties. We report here the synthesis, characterization, and reactivity of a 1,4,2,3-diazadiborole species, 2, featuring an unprecedented 6π-aromatic BN-heterocyclic moiety that is isoelectronic to cyclopentadienide (Cp-). Bearing an unsymmetrical B=B entity, 2 exhibits reactivity toward oxidants, protic reagents, electrophiles, and unsaturated substrates. This reactivity facilitates the synthesis of a variety of novel mono- and bicyclic organoboron derivatives through mechanisms including ring retention, cleavage/recombination, annulation, and expansion. These findings reveal innovative synthetic routes to BN-embedded aromatic compounds via desymmetrization, affording unique building blocks for synthetic chemistry.

BN Analogue of Butadiyne: A Platform for Dinitrogen Release and Reduction.

Exploration of the metallomimetic chemistry of main group elements is of the utmost importance from the perspective of both fundamental research and potential applications. Here, we report the synthesis, bonding analysis, and reactivities of an isolable diiminoborane, Mes*B≡N─N≡BMes* (Mes* = 2,4,6-tri-tert-butylphenyl) (1), a BN analogue of butadiyne. This species is characterized by a conjugated B≡N─N≡B moiety, a structural feature that enables the controlled release of N2 when it is exposed to organic nitriles. Furthermore, the N2 unit in 1 could be reduced to an ammonium salt via cleavage of the BN triple bond. Our work shows a rare example of an unsaturated BN system, serving as a platform for both the release and reduction of N2. This discovery opens new pathways and holds substantial influence on the future design of functional main group N2 species.

Derivatization of an Alkylideneborane with B═C Bond Cleavage.

We present the synthesis, structural characterization, and reactivity of alkylideneborane 2, supported by π-donating N-heterocyclic imino and σ-donating N-heterocyclic carbene (NHC) ligands. The incorporation of these ligands effectively weakens the B═C bond strength, leading to enhanced reactivity. Consequently, selective cleavage of the B═C bond can be achieved using pyridine-N-oxide, sulfur, and selenium, resulting in the formation of 1,3-dioxa-2,4-diboretane 3, thioxoborane 4, and selenoborane 5, respectively. Furthermore, intriguing B═C bond insertions with CO2 and CS2 are observed, affording zwitterionic borenium/fluorenide 6 and dithiaboretane 7. The former species 6 is readily converted to transient oxoborane and imidazolium enolate, showcasing the bora-Wittig reaction of alkylideneborane. This investigation highlights the potential of alkylideneborane as a versatile building block for synthesizing novel organoboron compounds through unconventional transformations.

Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases.

This report unveils an advancement in the formation of a Lewis superacid (LSA) and an organic superbase by the geometrical deformation of an organoboron species towards a T-shaped geometry. The boron dication [2]2+ supported by an amido diphosphine pincer ligand features both a large fluoride ion affinity (FIA>SbF5 ) and hydride ion affinity (HIA>B(C6 F5 )3 ), which qualifies it as both a hard and soft LSA. The unusual Lewis acidic properties of [2]2+ are further showcased by its ability to abstract hydride and fluoride from Et3 SiH and AgSbF6 respectively, and effectively catalyze the hydrodefluorination, defluorination/arylation, as well as reduction of carbonyl compounds. One and two-electron reduction of [2]2+ affords stable boron radical cation [2]⋅+ and borylene 2, respectively. The former species has an extremely high spin density of 0.798e at the boron atom, whereas the latter compound has been demonstrated to be a strong organic base (calcd. pKBH + (MeCN)=47.4) by both theoretical and experimental assessment. Overall, these results demonstrate the strong ability of geometric constraining to empower the central boron atom.

Unveiling Hetero-Enyne Reactivity of Aryliminoboranes: Dearomative Hetero-Diels-Alder-Like Reactions.

Being isoelectronic with alkynes, iminoboranes with a polar B≡N triple bond have been exclusively investigated as a potent 1,2-dipole in synthetic chemistry. Herein, we disclose the unprecedented reactivity of aryliminoboranes via the BNCC π conjugation, namely hetero-enyne behavior. This allows for facile dearomative Diels-Alder-like reactions of aryliminoboranes with aldehydes. This cycloaddition features mild conditions, is catalyst-free, and has a broad substrate scope and good functional group tolerance. Kinetic and computational studies reveal its second-order reaction and concerted cyclization mechanism. This report unveils new synthetic application of iminoboranes beyond their classical reaction patterns.

Crystalline Neutral Diboron Analogues of Cyclopropanes.

Although Schleyer's computations in 1979 predicted that the ground state of the parent diborirane features a planar-tetracoordinate carbon atom (anti van't Hoff-Le Bel geometry), this work demonstrates that substitution of C coupled with N-heterocyclic carbene (NHC) coordination provides access to isolable diborirane derivatives 3 and 4 with van't Hoff-Le Bel geometry. Species 3 and 4 are isoelectronic with cyclopropane and the highly strained B2 C rings feature 2c-2e bent σ bonds. Consequently, the B-B and B-C bonds in 3 are cleaved in the presence of hydride, proton, and chalcogens. The former two reactions gave NHC-coordinated fluorenyldihydridoborane 5 and dichlorofluorenylborane 6, respectively, whereas the latter transformations afforded novel thiaborirane 8 and selenaborirane 9. In addition, transfer hydrogenation of 3 with ammonia borane (H3 N⋅BH3 ) led to the formation of (µ-hydrido)diborane 7 via selective cleavage of the B-B bond. These reactivities show potential for their future application in organic synthesis.

Boraiminolithium: An Iminoborane-Transfer Reagent.

BN/CC isosterism can give rise to attractive molecules with unique physical or chemical properties. We report here the synthesis, characterization, and reactivities of the boraiminolithium species 2, a room-temperature-stable crystalline solid accessible through a facile dehydrohalogenation/deprotonation reaction. This species, bearing a polarized B≡N triple bond and an anionic N center, is the first example of a BN analogue to the well-known alkynyllithium molecules (lithium acetylides). It has demonstrated a remarkable ability for iminoborane-transfer reactions, which allows for the isolation of a series of unprecedented N-functionalized iminoboranes as well as novel main-group heterocycles. Stable boraiminolithium reagents may become powerful tools in the exploration of new BN-containing building blocks for synthetic chemistry and materials science.

Facile Access to Alkylideneborane and Diborabutadiene N-Heterocyclic Carbene Complexes.

A facile route to synthesis of B═C double-bonded systems has been developed. Specifically, both dibromofluorenylborane (FluH-BBr2) and a 1,1-dibromo-2,2-difluorenyldiborane/dimethyl sulfide adduct [(FluH)2B-BBr2(SMe2)] could be smoothly dehydrobrominated and subsequently coordinated by N-heterocyclic carbenes (NHCs) with formation of the respective alkylideneborane 1 and diborabutadiene 3. The electronic structures of 1 and 3 are interrogated and compared with those of base-free counterparts through density functional theory calculations.

NiCo alloy/C nanocomposites derived from a Ni-doped ZIF-67 for lightweight microwave absorbers.

In this work, we prepared NiCo alloy/C with rhombic dodecahedron structure and superior microwave absorption performance by using ZIF-67 as the raw material. The rhombic dodecahedron NiCo alloy/C was with rough particles on the surface was photographed by field emission scanning electron microscopy. By adjusting the doping amount of Ni and the temperature of pyrolysis, improved the impedance matching of NiCo alloy/C. Specifically, NiCo alloy/C exhibits a minimum reflection loss of -65.48 dB at 13.48 GHz, while the thickness is 1.63 mm. Defects introduced in the Ni doping process and the special rhombic dodecahedral structure can cause multiple loss mechanisms. Therefore, this NiCo alloy/C composite has the potential to be a potential microwave absorber material with lightweight and high microwave absorption properties.

New Approaches to N-Heterocyclic-Carbene-Coordinated Iminoborane and Borenium Species.

The synthesis, characterization, and reactivity of an iminoborane-N-heterocyclic carbene (NHC) adduct were described. The reaction of DmpNHB(OEt)Br [1; Dmp = 2,6-bis(2,4,6-trimethylphenyl)phenyl] with 2 equiv of 1,3-diimethyl-4,5-dimethylimidazol-2-ylidene (IMe4) resulted in the formation of an iminoborane-NHC complex 2. Both X-ray analysis and density functional theory calculations revealed the double-bond character of the B═N bond in 2. Interestingly, compared with the corresponding Lewis-base-free iminoborane, 2 features a nitrogen atom with increased electron density, which could be attributed to coordination of the NHC. Similar to the isoelectronic species imine, this nitrogen center in 2 can be easily attacked by electrophiles. Indeed, the reaction of 2 with trimethylsilyl triflate (Me3SiOTf) afforded an NHC-stabilized borenium cation 3, representing a facile strategy to prepare cationic tricoordinate boron species.

Bifurcated Hydrogen-Bond-Stabilized Boron Analogues of Carboxylic Acids.

The reactivity of a bulky m-terphenylboronic acid, DmpB(OH)2 [1; Dmp = 2,6-bis(2,4,6-trimethylphenyl)phenyl], toward three different N-heterocyclic carbenes has been examined. The reaction of 1 with 1 equiv of bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) leads to the formation of a hydrogen-bonded carbene boronic acid adduct, 2, featuring strong O-H···C contacts. In contrast, more basic 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IPr2Me2) and 1,3-di-tert-butylimidazol-2-ylidene (ItBu) deprotonate 1 smoothly to afford the rare anionic boranuidacarboxylic acids 3 and 4, respectively. Structural determination reveals that 3 and 4 bear unprecedented bifurcated hydrogen bonds with a BO- unit as a double hydrogen-bond acceptor, which contribute significantly to stabilization of the highly reactive B═O double bond. Quantum-mechanical calculations were conducted to disclose the unique electronic properties of the multiple bonds, as well as the important hydrogen bonds in these compounds.

Formation of Boron-Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L2PhB: (L = Oxazol-2-ylidene).

The reactivity of L2PhB: (1; L = oxazol-2-ylidene) as well as its transition-metal (chromium and iron) complexes toward main-group substrates have been systematically examined, which led to the construction of B-E (E = C, Ga, Cl, H, F, N) bonds. The combination of 1 and triethylborane smoothly captured carbon dioxide concomitant with the formation of B-C and B-O bonds. The soft basic boron center in 1 readily reacted with soft acidic gallium trichloride (GaCl3) to afford the extremely stable adduct 4 involving a B-Ga dative bond. Electrophilic alkylation of a neutral tricoordinate organoboron was first achieved by the treatment of 1 with dichloromethane and methyl trifluoromethanesulfonate (MeOTf), both of which afforded ionic species featuring an additional B-C bond. Comparatively, redox reactions took place when halides of heavier elements such as germanium dichloride, dichlorophenylphosphine, and chlorodiphenylbismuth were employed as substrates, from which cationic species 7 bearing a B-Cl bond was obtained. In addition, reactions of metal complexes [2, Cr(1)(CO)5; 8, Fe(1)(CO)4] with cationic electrophiles were investigated. With HOTf and FN(SO2Ph)2, the corresponding ionic species featuring a B-H bond (9) and a B-F bond (10) were formed via a formal electrophilic substitution reaction, whereas the reaction of 1 with F·Py-BF4 resulted in the formation of a dicationic boron species 11 with a newly formed B-N bond.

Isolation of a Diborane(6) Dication: Formation and Cleavage of an Electron-Precise B(sp(3))-B(sp(3)) Bond.

One-electron oxidation of organoboron L2PhB: 1 (L = oxazol-2-ylidene) afforded a dicationic diborane(6) species [L2PhB-BPhL2]·2X (X = OTf, BF4, AlCl4) 3, representing a new strategy to construct a B(sp(3))-B(sp(3)) covalent bond. Each boron atom in 3 is in the formal oxidation state +II, and tetracoordinate with a Ph group and two oxazol-2-ylidenes. The cyclic voltammetry of 3 shows irreversible reduction and oxidation. Indeed, two-electron reduction of 3 with potassium graphite (KC8) afforded 1, making a fully reversible 1 ↔ 3 redox system, whereas two-electron oxidation with AuCl produced a boronium [L2PhBCl]OTf 4. Moreover, the reactions of 3 with isonitrile derivatives RNC: under heating conditions gave a cyano-substituted boronium [L2PhBCN]BF4 5 and a 2-boranyl-indole derivative 6, depending on the substituent R. The proposed reaction mechanism involves a borinylium radical 1(•+) which is generated via a homolytic cleavage of the B-B bond of 3.

Serendipitous Observation of AlI Insertion into a C-O Bond in L2 PhB (L=Oxazol-2-ylidene).

Oxidative addition of the C-O bond in L2 PhB: (L=oxazol-2-ylidene) to an AlI center induced ring expansion of an oxazol-2-ylidene ring, affording a unique organoboron species formally involving either an Al, N, O mixed heterocyclic carbene or anionic (amino)(boryl)carbene fragment.

Azaborabutadienes: Synthesis by Metal-Free Carboboration of Nitriles and Utility as Building Blocks for B,N-Heterocycles.

Metal-free regioselective carboboration of arylnitriles with L2 PhB: (1: L=oxazol-2-ylidene) catalyzed by Et3 B afforded the unprecedented acyclic 2-aza-4-borabutadienes 2, thus demonstrating a new strategy to construct a B,C,N-mixed π-system involving B=C and C=N bonds. Thermal isomerization of 2 gave C-borylimines (3), and diverse reactivity of 2 a towards several substrates, such as H+ , F+ , O2 , S, Se, and isonitriles, allowed construction of boron-containing heterocycles with various ring sizes, thus illustrating the utility of 2 as a synthetic building block.

Isolation of a bis(oxazol-2-ylidene)-phenylborylene adduct and its reactivity as a boron-centered nucleophile.

An isolable phenylborylene species supported by two oxazol-2-ylidene ligands was synthesized and structurally characterized. Computational studies revealed the presence of lone-pair electrons on the boron atom in this molecule; therefore, there are eight electrons around the three-coordinate boron center. The nucleophilic property was confirmed by the reactions with trifluoromethanesulfonic acid and [(thf)Cr(CO)5], which gave the corresponding conjugate acid and a chromium-borylene complex, respectively.

A broadband 3D microtubular photodetector based on a single wall carbon nanotube-graphene heterojunction.

In this paper, a three-dimensional (3D) photodetector based on a single wall carbon nanotube (SWCNT) and graphene heterojunction has been fabricated by a self-rolled-up process. In the designed structure, graphene acted as the conductive channel and SWCNTs absorbed the incident light ranging from the visible to near-infrared bands. Compared to planar (two-dimensional, 2D) devices, 3D microcavities provided a natural resonant cavity to enhance the optical field, which improved the photoresponsivity. This 3D heterojunction photodetector realized a broadband photodetection from 470 to 940 nm with an ultrahigh photoresponsivity of 4.9 × 104 A W-1 (@ 590 nm) and 1.9 × 104 A W-1 (@ 940 nm), a fast photoresponse speed of 1.6 ms, and an excellent sensitivity of 2.28 × 1011 Jones. Besides, the fabricated photodetector showed favorable mid-infrared detection with a photoresponsivity of 3.08 A W-1 at 10.6 µm. Moreover, the photodetector exhibited a promising room-temperature imaging capability. The 3D heterojunction photodetector would provide a feasible pathway to realize graphene-based photodetectors with high performance and could be extended to be integrated with other light absorptive materials.

A Novel Terahertz Detector Based on Asymmetrical FET Array in 55-nm Standard CMOS Process.

This paper reports a novel, one-dimensional dense array of asymmetrical metal-oxide-semiconductor field-effect-transistor (MOSFET) THz detector, which has been fabricated in GlobalFoundries 55-nm CMOS technology. Compared with other technologies, the Si-based complementary metal-oxide-semiconductor (CMOS) dominates in industrial applications, owing to its easier integration and lower cost. However, as the frequency increases, the return loss between the antenna and detector will increase. The proposed THz detector has a short-period grating structure formed by MOSFET fingers in the array, which can serve as an effective antenna to couple incident THz radiation into the FET channels. It not only solved the problem of return loss effectively, but also greatly reduced the detector area. Meanwhile, since the THz signal is rectified at both the source and drain electrodes to generate two current signals with equal amplitude but opposite directions, the source drain voltage is not provided to reduce the power consumption. This leads to a poor performance of the THz detector. Therefore, by using an asymmetric structure for the gate fingers position to replace the source drain voltage, the performance of the detector in the case of zero power consumption can be effectively improved. Compared with the symmetrical MOSFET THz detector, Rv is increased by 183.3% and NEP is decreased by 67.7%.

Bimodal-Structured 0.9KNbO3-0.1BaTiO3 Solid Solutions with Highly Enhanced Electrocaloric Effect at Room Temperature.

0.9KNbO3-0.1BaTiO3 ceramics, with a bimodal grain size distribution and typical tetragonal perovskite structure at room temperature, were prepared by using an induced abnormal grain growth (IAGG) method at a relatively low sintering temperature. In this bimodal grain size distribution structure, the extra-large grains (~10-50 µm) were evolved from the micron-sized filler powders, and the fine grains (~0.05-0.35 µm) were derived from the sol precursor matrix. The 0.9KNbO3-0.1BaTiO3 ceramics exhibit relaxor-like behavior with a diffused phase transition near room temperature, as confirmed by the presence of the polar nanodomain regions revealed through high resolution transmission electron microscope analyses. A large room-temperature electrocaloric effect (ECE) was observed, with an adiabatic temperature drop (ΔT) of 1.5 K, an isothermal entropy change (ΔS) of 2.48 J·kg-1·K-1, and high ECE strengths of |ΔT/ΔE| = 1.50 × 10-6 K·m·V-1 and ΔS/ΔE = 2.48 × 10-6 J·m·kg-1·K-1·V-1 (directly measured at E = 1.0 MV·m-1). These greatly enhanced ECEs demonstrate that our simple IAGG method is highly appreciated for synthesizing high-performance electrocaloric materials for efficient cooling devices.