To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks,Pd-catalyzed one-pot reactions between pyridyl-substituted nido...To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks,Pd-catalyzed one-pot reactions between pyridyl-substituted nidocarboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds:3a-3f,4a-4d.The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy,single-crystal X-ray diffraction,and high-resolution mass spectrometry,and a plausible reaction mechanism was proposed.Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity.Furthermore,these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.CCDC:2481988,3c,2481990,3f,2481986,4d.展开更多
Using the experimentally known aromatic icosahedral superatoms I_(h)B_(12)H_(12)2−and D_(5d)1,12-C_(2)B_(10)H_(12)as building blocks and based on extensive density functional theory calculations,we predict herein a se...Using the experimentally known aromatic icosahedral superatoms I_(h)B_(12)H_(12)2−and D_(5d)1,12-C_(2)B_(10)H_(12)as building blocks and based on extensive density functional theory calculations,we predict herein a series of core–shell superpolyhedral boranes and carboranes in a bottom-up approach,including the high-symmetry Th B_(12)@B_(152)H_(72)2−(2),C2h C_(2)B_(10)@B_(152)H_(72)(3),D_(3d)B_(12)@B_(144)H_(66)(4),I_(h)B_(12)@C_(24)B_(12)0H_(72)2−(6),and D_(5d)C_(2)B_(10)@C_(24)B_(12)0H_(72)(7).More interestingly,the superatom-assembled linear D2h B_(36)H_(32)^(2−)(8),close-packed planar D_(3d)B_(84)H_(60)^(2−)(10),and nearly close-packed core−shell D_(3d)B_(12)@B144H_(6)6(4)can be extended periodically to form the one-dimensional(1D)α-rhombohedral borane nanowire B_(12)H_(10)(Pmmm)(9),two-dimensional(2D)α-rhombohedral monolayer borophane B_(12)H_(6)(P m1)(11),and the experimentally known three-dimensional(3D)α-rhombohedral boron(R m)(12)which can be viewed as an assembly of the monolayer B_(12)H_(6)(11)staggered in vertical direction,setting up a bottom-up strategy to form low-dimensional boron-based nanomaterials from their borane“seeds”via partial or complete dehydrogenations.Detailed bonding analyses indicate that the high stability of these nanostructures originates from the spherical aromaticity of their icosahedral B_(12)or C_(2)B_(10)structural units which possess the universal skeleton electronic configuration of 1S21P61D101F8 following the Wade’s n+1 rule.The infrared(IR)and Raman spectra of the most-concerned neutral B_(12)@B144H_(6)6(4)and C_(2)B_(10)@C_(24)B_(12)0H_(72)(7)are computationally simulated to facilitate their experimental characterizations.展开更多
Persistent homology is a powerful and novel tool for quantifying the inherent topological features of structure. In this work, we used the persistent homology for the first time to study the closo-carboranes C2Bn-2Hn(...Persistent homology is a powerful and novel tool for quantifying the inherent topological features of structure. In this work, we used the persistent homology for the first time to study the closo-carboranes C2Bn-2Hn(n = 5~20) and their parent structures closo-boranes dianions BnHn2-(n = 5~20), where multiple elements are present. All these structures are first investigated with the standard Vitoris-Rips complex. We interpret all barcodes representation and associate them with structural details. By means of average bar length, a linear regression model was established to construct the relationship between persistent homology features and molecular stability, which was expressed by the relative energies. For closo-boranes dianions, we only use B atom set since B and H atoms are in pairs. The average lengths of β0, β1 and β2 bars are used as the features for linear regression, and excellent correlation coefficient(0.977) between the values predicted by persistent homology and those by quantum calculations was achieved. For closo-carboranes, C–B atom set(ignore the differences in the atoms), B atom set and C atom set were considered to get the persistent homology features(since there were only two C atoms in C2Bn-2Hn, only β0 bars were considered), and seven average bar lengths were calculated, respectively. Pearson coefficient of 0.937 was obtained. We found that the stability of carboranes showed a high linear correlation with the characteristics generated from topological bars in H0, H1 and H2. The results show that the topological information generated by persistent homology can be extended and applied to multi-element systems.展开更多
Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords ...Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords unprecedented C,B-substituted carborane-fused-pyridone derivatives, whereas the use of terminal alkynes leads to B–H/C(sp)–H dehydrocoupling products. The isolation and structural identification of a notably stable Cu(Ⅰ) intermediate shed light on the reaction mechanism, which is proposed to involve a Cu(Ⅲ) intermediate.展开更多
Though transition metal-catalyzed cage BH methylation has been well documented, catalytic alkylation of cage BH bonds remained elusive because transition metal alkyl complexes are prone to undergo β-H elimination. We...Though transition metal-catalyzed cage BH methylation has been well documented, catalytic alkylation of cage BH bonds remained elusive because transition metal alkyl complexes are prone to undergo β-H elimination. We report herein a highly efficient 8-aminoquinoline-assisted nickel-catalyzed regioselective cage B(3,4,5,6)-H tetra-alkylation of o-carboranes employing unactivated alkyl bromides as alkylating agents in the absence of any oxidants, leading to the preparation of a class of tetra-alkylated o-carboranes with a broad substrate scope in good to very high yields. This method opens new avenues for oxidant-free, direct, efficient, sustainable, and regioselective multiple B–H alkylation of carboranes via base metal catalysis.展开更多
This work describes a general method for the synthesis of a series of sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron-centered carbora...This work describes a general method for the synthesis of a series of sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron-centered carboranyl radicals.Such hypervalent boron radicals are generated by a visible-light-promoted Pd(O)/Pd(I)pathway.They are useful intermediates and can be trapped by disulfides and phenylselenyl chloride for the convenient construction of B-S/Sebonds.展开更多
We report herein a practical approach for regio-selective B—H/C—H bond activation at azo-substituted carboranes. The reaction proceeded through Iridium(III)-induced selective B—H/C—H bond activations based on an a...We report herein a practical approach for regio-selective B—H/C—H bond activation at azo-substituted carboranes. The reaction proceeded through Iridium(III)-induced selective B—H/C—H bond activations based on an azo directing group. Through this strategy, a series of mononuclear, trinuclear and tetranuclear cyclometalated iridium complexes containing Cp*Ir—B or Cp*Ir—C bonds were successfully isolated in a high yield. In this work, efficient routes are developed through one-pot reactions to prepare polynuclear organometallic complexes.展开更多
Thermally activated delayed fluorescence(TADF)materials driven by a through-space charge transfer(TSCT)mechanism have garnered wide interest.However,access of TSCT-TADF molecules with longwavelength emission remains a...Thermally activated delayed fluorescence(TADF)materials driven by a through-space charge transfer(TSCT)mechanism have garnered wide interest.However,access of TSCT-TADF molecules with longwavelength emission remains a formidable challenge.In this study,we introduce a novel V-type DA-D-A’emitter,Trz-mCzCbCz,by using a carborane scaffold.This design strategically incorporates carbazole(Cz)and 2,4,6-triphenyl-1,3,5-triazine(Trz)as donor and acceptor moieties,respectively.Theoretical calculations alongside experimental validations affirm the typical TSCT-TADF characteristics of this luminogen.Owing to the unique structural and electronic attributes of carboranes,Trz-mCzCbCz exhibits an orange-red emission,markedly diverging from the traditional blue-to-green emissions observed in classical Cz and Trz-based TADF molecules.Moreover,bright emission in aggregates was observed for Trz-mCzCbCz with absolute photoluminescence quantum yield(PLQY)of up to 88.8%.As such,we have successfully fabricated five organic light-emitting diodes(OLEDs)by utilizing Trz-mCzCbCz as the emitting layer.It is important to note that both the reverse intersystem crossing process and the TADF properties are profoundly influenced by host materials.The fabricated OLED devices reached a maximum external quantum efficiency(EQE)of 12.7%,with an emission peak at 592 nm.This represents the highest recorded efficiency for TSCT-TADF OLEDs employing carborane derivatives as emitting layers.展开更多
Herein,we describe the synthesis and characterization of four complexes containing half-sandwich iridium metal-corner which were obtained through the interaction between known complexes Cp*MCl(o-C_(2)B_(10)H_(11)CS_(2...Herein,we describe the synthesis and characterization of four complexes containing half-sandwich iridium metal-corner which were obtained through the interaction between known complexes Cp*MCl(o-C_(2)B_(10)H_(11)CS_(2))(M=Ir/Rh,Complex 1a and 1b)and corresponding reagents.An incomplete cubane-like complex[Cp*Ir(o-C_(2)B_(10)H_(11)CHS_(2))]_(2)(Complex 2)has been prepared through the reaction between 1a and LiBH4 or NaBH4.Co-thermolysis between 1a and BH_(3)·THF in toluene produces a trimer metallacycle complex[Cp*Ir(o-C_(2)B_(10)H_(10)CS_(2))]_(3)(Complex 3),while its rhodium analogue[Cp*Rh(o-C_(2)B_(10)H_(10)CS_(2))]_(3)(Complex 4)can be prepared through BiPh_(3)-assisted dechlorination reaction of 1b.Furthermore,the oxidative addition reaction of 1a towards SnCl_(2)generates a mononuclear complex Cp*Ir(SnCl_(3))(o-C_(2)B_(10)H_(11)CS_(2))(Complex 5)with a direct Sn-Ir bond.These complexes have been characterized,including X-Ray single crystal diffraction,NMR spectroscopy and elemental analysis methods.展开更多
The complex [closo-3,3-（PPh<sub>3</sub>）<sub>2</sub>-3-H-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]has a rich derivative chemistrythat is currently ...The complex [closo-3,3-（PPh<sub>3</sub>）<sub>2</sub>-3-H-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]has a rich derivative chemistrythat is currently under active investigation.The resultant compound shows an increasing stabilitythat is often associated with metallocarboranes.This paper deals with the novel and the produc-tion area of carborane complexes of transition metals.The paper indicates that some reactions can easily proceed and the resulting compound hassome new properties and uses.K[18-crown-6][closo-3-Ph<sub>3</sub>P-3-CH<sub>2</sub>Ph-3-Br-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]can be synthesized by the reaction of K[18-crown-6][（Ph<sub>3</sub>P）<sub>2</sub>RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]withbromo-toluene under the condition of dry benzene.IR and <sup>1</sup>H,<sup>11</sup>B,<sup>31</sup>p nuclear magnetic reso-nance and elemental analysis comfirm the structure for this species with one carborane groupbonded to the central metal.展开更多
In this study, two fluorinated polyurethanes（FPU） containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer（HDI trimer） with fluorin...In this study, two fluorinated polyurethanes（FPU） containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer（HDI trimer） with fluorinated polyesters（CFPETs） having hydroxyl-terminated carborane groups at room temperature. The structures of carborane fluorinated polyesters（CFPETs） and polyurethanes（CFPUs） were characterized by gel permeation chromatography（GPC）, Fourier transform infrared（FTIR） spectroscopy and nuclear magnetic resonance（NMR） measurements. The thermal stability, mechanical properties, Shore A hardness, solvent resistance and acid-alkali resistance of the carborane fluorinated polyurethane films were also studied. Thermogravimetric analysis（TGA） tests manifested that the introduction of carborane groups into the main chain of fluorinated polyurethane endowed the obtained fluorinated polyurethane with excellent thermal stability. The thermal decomposition temperature of carborane fluorinated polyurethane（CFPU） increased by 190 °C compared with that of the carborane-free fluorinated polyurethane（FPU）. Even at 800 °C, CFPU showed the char yield of 66.5%, which was higher than that of FPU（34.3%）. The carborane-containing fluorinated polyurethanes also showed excellent chemical resistance and prominent mechanical property even after the cured films being immersed into Jet aircraft oil or 37% HCl for 168 h or at high temperature（700 °C）. It is found that the structural characteristics of carborane group and the compacted structure of CFPU effectively improve the thermal stability, mechanical property, solvent resistance and acid-alkali resistance of the carborane-free fluorinated polyurethane. These excellent properties make CFPU as the useful raw materials to prepare the high temperature resistant coatings or adhesives for automotive engines, engine or fuel tank of aircraft and other equipment working in high-temperature or high concentrations of acid-alkali environments.展开更多
Carborane bisphenol novolacs （3 and 4） were synthesized in the presence of acid catalyst from carborane bisphenols （5 and 6） and formaldehyde. Further epoxidization of carborane bisphenol novolacs with epichlorohy...Carborane bisphenol novolacs （3 and 4） were synthesized in the presence of acid catalyst from carborane bisphenols （5 and 6） and formaldehyde. Further epoxidization of carborane bisphenol novolacs with epichlorohydrin gave carborane bisphenol epoxy novolacs （1 and 2）. The molecular weight and epoxy value of obtained resins were determined using the molecular weight of their precursors. The epoxy values of 1 and 2 were 0.48 and 0.52 respectively, higher than the maximum theoretical epoxy value （0.45） of difunctional carborane bisphenol epoxy resins. FTIR and NMR were utilized to characterize 1 and 2. The curing behaviors were also studied by DSC and the optimized curing conditions were obtained. TGA analysis indicated that carborane moiety could shield its adjacent organic structures against initial decomposition. On the other hand, B--H on carborane cage could react with oxygen to form a three-dimensional network linked by B--O--B and B--C bonds, which further blocked the movement of formed radicals and thus the degradation process was inhibited.展开更多
o-Carborane-containing poly（hydroxy ethers）（P1, P2 and P3） were synthesized via ＂advancement reaction＂ of o-carborane-containing bisphenol（4） and diglycidyl ether of bisphenols（DGEBA and 1）. FTIR and 1^H^-,...o-Carborane-containing poly（hydroxy ethers）（P1, P2 and P3） were synthesized via ＂advancement reaction＂ of o-carborane-containing bisphenol（4） and diglycidyl ether of bisphenols（DGEBA and 1）. FTIR and 1^H^-, 13^C^-, and 11^ B-NMR were utilized to characterize the obtained polymers. TGA test was conducted under nitrogen and air. It is found that the shielding effect of carborane moiety on its adjacent aromatic structures contributes to high initial decomposition temperatures, while oxygen in air has an adverse effect on the initial decomposition temperature. The oxygen can combine with polymer chain to form peroxide and hydroperoxide groups, which are more reactive during the degradation process. Besides, o-carborane-containing poly（hydroxy ethers） have high char yield at elevated temperatures. The boron atom combines with oxygen from the polymer structure or/and from air, thus to form a three-dimensional network linked with B―O―B and B―C bonds, and retain the polymer weight to a large extent.展开更多
The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, ...The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, (MoK? = 5.30 cm1, F(000) = 874, R = 0.0622 and Rw = 0.1538 for 1641 observed reflections with I > 2(I). The ionic complex of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)2(THF)] and the tetrahedral cation of [Li(THF)4]+. The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.展开更多
Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabiliti...Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric effects.These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group compounds.This review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based ligands.Achievements and perspectives in this new and flourishing field are discussed in this review.展开更多
Halfsandwich iron dicarbonyl complex [η 5-C5H3（t-Bu）2]Fe（CO）2Cl（1） reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10（2） to give a binuclear iron carborane complex [η 5-C5H3（t-Bu）2]2Fe2（CO）3&...Halfsandwich iron dicarbonyl complex [η 5-C5H3（t-Bu）2]Fe（CO）2Cl（1） reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10（2） to give a binuclear iron carborane complex [η 5-C5H3（t-Bu）2]2Fe2（CO）3·Se2C2B 10H 10（3）. The X-ray diffraction analysis of complex 3 reveals that one of the iron atoms is chiral.展开更多
A new compound [CpCo（Se2C2BIoH9）CH2C（O）C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic...A new compound [CpCo（Se2C2BIoH9）CH2C（O）C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481（10）, b = 24.6600（12）, c = 25.7430（14） A, β = 100.863（3）°, C42H57B30Co306Se6＂CH2C12＂0.25H20, Mr = 1722.16, V = 6825.6（8） A3, Dc= 1.676 g/cm3, Z = 1 and F（000） = 3346. The molecular structure shows a 1：1 ratio product of the two reactants of 16e half-sandwich complex CpCo（Se2C2B10H10） and alkyne 1-（2-furyl）-2-propyn-l-one. The hydrogen atom in the B（3） position of CpCo（Se2C2B10HIo） has been activated and migrated to the terminal carbon of 1-（2-furyl）- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds.展开更多
Here we describe the cation reduction and comproportionation as novel routes to synthesize electrolytes for rechargeable Mg-ion batteries.Reduction of the ammonium cation in[HNMe_(3)^(1+)][HCB_(11)H_(11)^(1-)]with met...Here we describe the cation reduction and comproportionation as novel routes to synthesize electrolytes for rechargeable Mg-ion batteries.Reduction of the ammonium cation in[HNMe_(3)^(1+)][HCB_(11)H_(11)^(1-)]with metallic Mg affords the halide free carborane salt[Mg^(2+)][HCB_(11)H_(11)^(1-)]2.Comproportionation of[Mg^(2+)][HCB_(11)H_(11)^(1-)]_(2) with MgPh_(2) affords the novel monocationic electrolyte[MgPh^(1+)][HCB_(11)H_(11)^(1-)],which reversibly deposits/strips Mg with a remarkable oxidative stability of 4.6 V vs.Mg^(0/+2).展开更多
Two anthracenyl-styrenyl-m-carborane triads(one non-iodinated on B,3,and one iodinated,4)were synthesized and characterized to be further linked to octavinylsilsesquioxane(OVS)via cross-metathesis,giving rise to the c...Two anthracenyl-styrenyl-m-carborane triads(one non-iodinated on B,3,and one iodinated,4)were synthesized and characterized to be further linked to octavinylsilsesquioxane(OVS)via cross-metathesis,giving rise to the corresponding hybrid materials 5 and 6.The crystal structure of the non-iodinated heterosubstituted-m-carborane 3 was analyzed by X-ray diffraction.Transmission electron microscopy images of pristine OVS and hybrids 5-6 show important differences in the morphology of the particles;whereas OVS forms cubic-like particles,5-6 have a spherical shape with a broad particle-size distribution.All compounds showed similar vibronic emission spectra in solution,with maxima around 415 nm,assigned to the locally excited state(LE)emission of the anthracene moiety.The similarity with the spectra of the free anthracene(λ_(em)=420 nm)suggested that only small electronic interactions between the anthracene units have taken place,and there is no influence of the iodo or styrene groups on the absorption properties.This is in agreement with the DFT calculations,where calculated oscillator strength corresponding to the transitions from iodo orbitals to the LUMO are weak and could not be observed experimentally.Noticeable,triads 3-4 exhibited exceptional fluorescence quantum yield values of around 100%in solution,that are comparable to those determined for their precursors 1-2,demonstrating that the influence of the styrene group is negligible.Linking these m-carborane derivatives to the OVS led to a significant decrease of quantum yields to 34-45%for 5-6 in solution.Moreover,the PL behavior in the aggregate state was investigated and the spectra of all compounds were very similar,showing emission red-shift with maxima around 455-459 nm.Remarkably,quite high fluorescence quantum yields were determined for 3-4((ϕ_(F)=26-31%)and 5-6(ϕ_(F)=27-36%)in the aggregated state.These data confirm that the m-carborane platform enhances the quantum efficiency of the anthracene in solution,without losing the emission properties in the aggregate state.If this affirmation is associated to other scattered examples on other fluorophores also linked to m-carborane existing in the literature,the former conclusion is reinforced.m-Carborane enhances the fluorescence quantum yield of the free fluorophore,but does not alter the energy of the participating states in the photoluminescence in solution.展开更多
In this study,we present the first synthesis of ferroelectric crystals where the carbon vertices of carboranes are substituted with cycloalkane groups.These crystals include 1,2-(1,3-propanediyl)-o-carborane(1)and 1,2...In this study,we present the first synthesis of ferroelectric crystals where the carbon vertices of carboranes are substituted with cycloalkane groups.These crystals include 1,2-(1,3-propanediyl)-o-carborane(1)and 1,2-(1,4-hexanediyl)-o-carborane(2),both of which exhibit relatively high Curie temperatures at 328.6 K and 320.6 K.Notably,to the best of our knowledge,this represents the first instance of ferroelectric crystals derived from modifications at the carbon vertex of carborane.This discovery provides a valuable new avenue for research into novel carborane-based ferroelectrics and holds promise for advancing the broader application of ferroelectric materials.展开更多
文摘To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks,Pd-catalyzed one-pot reactions between pyridyl-substituted nidocarboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds:3a-3f,4a-4d.The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy,single-crystal X-ray diffraction,and high-resolution mass spectrometry,and a plausible reaction mechanism was proposed.Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity.Furthermore,these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.CCDC:2481988,3c,2481990,3f,2481986,4d.
基金supported by the National Natural Science Foundation of China(Nos.22373061,21973057,and 22003034).
文摘Using the experimentally known aromatic icosahedral superatoms I_(h)B_(12)H_(12)2−and D_(5d)1,12-C_(2)B_(10)H_(12)as building blocks and based on extensive density functional theory calculations,we predict herein a series of core–shell superpolyhedral boranes and carboranes in a bottom-up approach,including the high-symmetry Th B_(12)@B_(152)H_(72)2−(2),C2h C_(2)B_(10)@B_(152)H_(72)(3),D_(3d)B_(12)@B_(144)H_(66)(4),I_(h)B_(12)@C_(24)B_(12)0H_(72)2−(6),and D_(5d)C_(2)B_(10)@C_(24)B_(12)0H_(72)(7).More interestingly,the superatom-assembled linear D2h B_(36)H_(32)^(2−)(8),close-packed planar D_(3d)B_(84)H_(60)^(2−)(10),and nearly close-packed core−shell D_(3d)B_(12)@B144H_(6)6(4)can be extended periodically to form the one-dimensional(1D)α-rhombohedral borane nanowire B_(12)H_(10)(Pmmm)(9),two-dimensional(2D)α-rhombohedral monolayer borophane B_(12)H_(6)(P m1)(11),and the experimentally known three-dimensional(3D)α-rhombohedral boron(R m)(12)which can be viewed as an assembly of the monolayer B_(12)H_(6)(11)staggered in vertical direction,setting up a bottom-up strategy to form low-dimensional boron-based nanomaterials from their borane“seeds”via partial or complete dehydrogenations.Detailed bonding analyses indicate that the high stability of these nanostructures originates from the spherical aromaticity of their icosahedral B_(12)or C_(2)B_(10)structural units which possess the universal skeleton electronic configuration of 1S21P61D101F8 following the Wade’s n+1 rule.The infrared(IR)and Raman spectra of the most-concerned neutral B_(12)@B144H_(6)6(4)and C_(2)B_(10)@C_(24)B_(12)0H_(72)(7)are computationally simulated to facilitate their experimental characterizations.
基金supported by the National Key R&D Program of China (2016YFB0700600)Soft Science Research Project of Guangdong Province (2017B030301013)+2 种基金Shenzhen Science and Technology Research Grant (ZDSYS201707281026184)supported in partial by NSF Grants DMS1721024,DMS1761320,IIS1900473NIH grants GM126189 and GM129004 Bristol-Myers Squibband Pfizer。
文摘Persistent homology is a powerful and novel tool for quantifying the inherent topological features of structure. In this work, we used the persistent homology for the first time to study the closo-carboranes C2Bn-2Hn(n = 5~20) and their parent structures closo-boranes dianions BnHn2-(n = 5~20), where multiple elements are present. All these structures are first investigated with the standard Vitoris-Rips complex. We interpret all barcodes representation and associate them with structural details. By means of average bar length, a linear regression model was established to construct the relationship between persistent homology features and molecular stability, which was expressed by the relative energies. For closo-boranes dianions, we only use B atom set since B and H atoms are in pairs. The average lengths of β0, β1 and β2 bars are used as the features for linear regression, and excellent correlation coefficient(0.977) between the values predicted by persistent homology and those by quantum calculations was achieved. For closo-carboranes, C–B atom set(ignore the differences in the atoms), B atom set and C atom set were considered to get the persistent homology features(since there were only two C atoms in C2Bn-2Hn, only β0 bars were considered), and seven average bar lengths were calculated, respectively. Pearson coefficient of 0.937 was obtained. We found that the stability of carboranes showed a high linear correlation with the characteristics generated from topological bars in H0, H1 and H2. The results show that the topological information generated by persistent homology can be extended and applied to multi-element systems.
基金supported by the Research Grants Council of The Hong Kong Special Administration Region(14304115,14305017)CUHK Direct Grant and Incentive Grant from Faculty of Science,CUHK
文摘Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed [4+2] annulation of carboranyl amides with internal alkynes affords unprecedented C,B-substituted carborane-fused-pyridone derivatives, whereas the use of terminal alkynes leads to B–H/C(sp)–H dehydrocoupling products. The isolation and structural identification of a notably stable Cu(Ⅰ) intermediate shed light on the reaction mechanism, which is proposed to involve a Cu(Ⅲ) intermediate.
基金supported by the Research Grants Council of the Hong Kong Special Administration Region (SRFS20214S05)。
文摘Though transition metal-catalyzed cage BH methylation has been well documented, catalytic alkylation of cage BH bonds remained elusive because transition metal alkyl complexes are prone to undergo β-H elimination. We report herein a highly efficient 8-aminoquinoline-assisted nickel-catalyzed regioselective cage B(3,4,5,6)-H tetra-alkylation of o-carboranes employing unactivated alkyl bromides as alkylating agents in the absence of any oxidants, leading to the preparation of a class of tetra-alkylated o-carboranes with a broad substrate scope in good to very high yields. This method opens new avenues for oxidant-free, direct, efficient, sustainable, and regioselective multiple B–H alkylation of carboranes via base metal catalysis.
基金supported by a grant from the Southern University of Science and Technology.
文摘This work describes a general method for the synthesis of a series of sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron-centered carboranyl radicals.Such hypervalent boron radicals are generated by a visible-light-promoted Pd(O)/Pd(I)pathway.They are useful intermediates and can be trapped by disulfides and phenylselenyl chloride for the convenient construction of B-S/Sebonds.
基金This work was supported by the National Natural Science Foun-dation of China(Nos.21531002,21720102004,22031003)the Shanghai Science Technology Committee(No.13JC1400600).
文摘We report herein a practical approach for regio-selective B—H/C—H bond activation at azo-substituted carboranes. The reaction proceeded through Iridium(III)-induced selective B—H/C—H bond activations based on an azo directing group. Through this strategy, a series of mononuclear, trinuclear and tetranuclear cyclometalated iridium complexes containing Cp*Ir—B or Cp*Ir—C bonds were successfully isolated in a high yield. In this work, efficient routes are developed through one-pot reactions to prepare polynuclear organometallic complexes.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BZ2022007)the National Natural Science Foundation of China(No.92261202)+1 种基金the Ministry of Science and Technology of the People’s Republic of China(No.2021YFE0114800)the Ministry of Science and Higher Education of the Russian Federation(No.075-15-2021-1027).
文摘Thermally activated delayed fluorescence(TADF)materials driven by a through-space charge transfer(TSCT)mechanism have garnered wide interest.However,access of TSCT-TADF molecules with longwavelength emission remains a formidable challenge.In this study,we introduce a novel V-type DA-D-A’emitter,Trz-mCzCbCz,by using a carborane scaffold.This design strategically incorporates carbazole(Cz)and 2,4,6-triphenyl-1,3,5-triazine(Trz)as donor and acceptor moieties,respectively.Theoretical calculations alongside experimental validations affirm the typical TSCT-TADF characteristics of this luminogen.Owing to the unique structural and electronic attributes of carboranes,Trz-mCzCbCz exhibits an orange-red emission,markedly diverging from the traditional blue-to-green emissions observed in classical Cz and Trz-based TADF molecules.Moreover,bright emission in aggregates was observed for Trz-mCzCbCz with absolute photoluminescence quantum yield(PLQY)of up to 88.8%.As such,we have successfully fabricated five organic light-emitting diodes(OLEDs)by utilizing Trz-mCzCbCz as the emitting layer.It is important to note that both the reverse intersystem crossing process and the TADF properties are profoundly influenced by host materials.The fabricated OLED devices reached a maximum external quantum efficiency(EQE)of 12.7%,with an emission peak at 592 nm.This represents the highest recorded efficiency for TSCT-TADF OLEDs employing carborane derivatives as emitting layers.
基金The National Science Foundation of China(22031003,21720102004)the Shanghai Science Technology Committee(19DZ2270100)。
文摘Herein,we describe the synthesis and characterization of four complexes containing half-sandwich iridium metal-corner which were obtained through the interaction between known complexes Cp*MCl(o-C_(2)B_(10)H_(11)CS_(2))(M=Ir/Rh,Complex 1a and 1b)and corresponding reagents.An incomplete cubane-like complex[Cp*Ir(o-C_(2)B_(10)H_(11)CHS_(2))]_(2)(Complex 2)has been prepared through the reaction between 1a and LiBH4 or NaBH4.Co-thermolysis between 1a and BH_(3)·THF in toluene produces a trimer metallacycle complex[Cp*Ir(o-C_(2)B_(10)H_(10)CS_(2))]_(3)(Complex 3),while its rhodium analogue[Cp*Rh(o-C_(2)B_(10)H_(10)CS_(2))]_(3)(Complex 4)can be prepared through BiPh_(3)-assisted dechlorination reaction of 1b.Furthermore,the oxidative addition reaction of 1a towards SnCl_(2)generates a mononuclear complex Cp*Ir(SnCl_(3))(o-C_(2)B_(10)H_(11)CS_(2))(Complex 5)with a direct Sn-Ir bond.These complexes have been characterized,including X-Ray single crystal diffraction,NMR spectroscopy and elemental analysis methods.
文摘The complex [closo-3,3-（PPh<sub>3</sub>）<sub>2</sub>-3-H-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]has a rich derivative chemistrythat is currently under active investigation.The resultant compound shows an increasing stabilitythat is often associated with metallocarboranes.This paper deals with the novel and the produc-tion area of carborane complexes of transition metals.The paper indicates that some reactions can easily proceed and the resulting compound hassome new properties and uses.K[18-crown-6][closo-3-Ph<sub>3</sub>P-3-CH<sub>2</sub>Ph-3-Br-3,1,2-RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]can be synthesized by the reaction of K[18-crown-6][（Ph<sub>3</sub>P）<sub>2</sub>RhC<sub>2</sub>B<sub>9</sub>H<sub>11</sub>]withbromo-toluene under the condition of dry benzene.IR and <sup>1</sup>H,<sup>11</sup>B,<sup>31</sup>p nuclear magnetic reso-nance and elemental analysis comfirm the structure for this species with one carborane groupbonded to the central metal.
基金financially supported by International Cooperative Project (Harbin Institute of Technology 2014DFR40370)International Cooperative Project (Wuxi HIT Limited Corporation & Research Institute of New Materials BZ2015024)
文摘In this study, two fluorinated polyurethanes（FPU） containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer（HDI trimer） with fluorinated polyesters（CFPETs） having hydroxyl-terminated carborane groups at room temperature. The structures of carborane fluorinated polyesters（CFPETs） and polyurethanes（CFPUs） were characterized by gel permeation chromatography（GPC）, Fourier transform infrared（FTIR） spectroscopy and nuclear magnetic resonance（NMR） measurements. The thermal stability, mechanical properties, Shore A hardness, solvent resistance and acid-alkali resistance of the carborane fluorinated polyurethane films were also studied. Thermogravimetric analysis（TGA） tests manifested that the introduction of carborane groups into the main chain of fluorinated polyurethane endowed the obtained fluorinated polyurethane with excellent thermal stability. The thermal decomposition temperature of carborane fluorinated polyurethane（CFPU） increased by 190 °C compared with that of the carborane-free fluorinated polyurethane（FPU）. Even at 800 °C, CFPU showed the char yield of 66.5%, which was higher than that of FPU（34.3%）. The carborane-containing fluorinated polyurethanes also showed excellent chemical resistance and prominent mechanical property even after the cured films being immersed into Jet aircraft oil or 37% HCl for 168 h or at high temperature（700 °C）. It is found that the structural characteristics of carborane group and the compacted structure of CFPU effectively improve the thermal stability, mechanical property, solvent resistance and acid-alkali resistance of the carborane-free fluorinated polyurethane. These excellent properties make CFPU as the useful raw materials to prepare the high temperature resistant coatings or adhesives for automotive engines, engine or fuel tank of aircraft and other equipment working in high-temperature or high concentrations of acid-alkali environments.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.JD-1512)
文摘Carborane bisphenol novolacs （3 and 4） were synthesized in the presence of acid catalyst from carborane bisphenols （5 and 6） and formaldehyde. Further epoxidization of carborane bisphenol novolacs with epichlorohydrin gave carborane bisphenol epoxy novolacs （1 and 2）. The molecular weight and epoxy value of obtained resins were determined using the molecular weight of their precursors. The epoxy values of 1 and 2 were 0.48 and 0.52 respectively, higher than the maximum theoretical epoxy value （0.45） of difunctional carborane bisphenol epoxy resins. FTIR and NMR were utilized to characterize 1 and 2. The curing behaviors were also studied by DSC and the optimized curing conditions were obtained. TGA analysis indicated that carborane moiety could shield its adjacent organic structures against initial decomposition. On the other hand, B--H on carborane cage could react with oxygen to form a three-dimensional network linked by B--O--B and B--C bonds, which further blocked the movement of formed radicals and thus the degradation process was inhibited.
基金financially supported by National Key R&D Program of China(No.2016YFB0302105)
文摘o-Carborane-containing poly（hydroxy ethers）（P1, P2 and P3） were synthesized via ＂advancement reaction＂ of o-carborane-containing bisphenol（4） and diglycidyl ether of bisphenols（DGEBA and 1）. FTIR and 1^H^-, 13^C^-, and 11^ B-NMR were utilized to characterize the obtained polymers. TGA test was conducted under nitrogen and air. It is found that the shielding effect of carborane moiety on its adjacent aromatic structures contributes to high initial decomposition temperatures, while oxygen in air has an adverse effect on the initial decomposition temperature. The oxygen can combine with polymer chain to form peroxide and hydroperoxide groups, which are more reactive during the degradation process. Besides, o-carborane-containing poly（hydroxy ethers） have high char yield at elevated temperatures. The boron atom combines with oxygen from the polymer structure or/and from air, thus to form a three-dimensional network linked with B―O―B and B―C bonds, and retain the polymer weight to a large extent.
基金Financially Supported by the National Natural Science Foundation of China (29974029, 29925101) and Special Funds for Major State Basic Research Projects of China (G1999064800)
文摘The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, (MoK? = 5.30 cm1, F(000) = 874, R = 0.0622 and Rw = 0.1538 for 1641 observed reflections with I > 2(I). The ionic complex of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)2(THF)] and the tetrahedral cation of [Li(THF)4]+. The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.
基金the National Natural Science Foundation of China(No.21901039)the Natural Science Foundation of Jiangsu Province(No.BK20190327)。
文摘Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric effects.These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group compounds.This review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based ligands.Achievements and perspectives in this new and flourishing field are discussed in this review.
基金Supported by the National Natural Science Foundation of China( No.2 99740 2 9,2 992 5 10 1) and Special Funds forMajor State Basic Research Projects of China( G19990 64 80 0)
文摘Halfsandwich iron dicarbonyl complex [η 5-C5H3（t-Bu）2]Fe（CO）2Cl（1） reacts with 1, 2-dilithium diseleno carborane Li2Se2C2B 10H 10（2） to give a binuclear iron carborane complex [η 5-C5H3（t-Bu）2]2Fe2（CO）3·Se2C2B 10H 10（3）. The X-ray diffraction analysis of complex 3 reveals that one of the iron atoms is chiral.
基金Project supported by the Science and Technology Research Project of Key Laboratory of Higher Institutions of Jiangxi Province(No.GJJl 1710)the Science and Technology Research Projects of the Education Department of Jiangxi Province(Nos.GJJ09376 and GJJ10613)+2 种基金the National Natural Science Foundation of China(21361022 and 21261020)the Scientific and Technological Landing Project of Higher Education of Jiangxi Province(No.KJLD12094)the Fourth Point of Specialty Construction College of Education Ministry(No.TS11524)
文摘A new compound [CpCo（Se2C2BIoH9）CH2C（O）C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481（10）, b = 24.6600（12）, c = 25.7430（14） A, β = 100.863（3）°, C42H57B30Co306Se6＂CH2C12＂0.25H20, Mr = 1722.16, V = 6825.6（8） A3, Dc= 1.676 g/cm3, Z = 1 and F（000） = 3346. The molecular structure shows a 1：1 ratio product of the two reactants of 16e half-sandwich complex CpCo（Se2C2B10H10） and alkyne 1-（2-furyl）-2-propyn-l-one. The hydrogen atom in the B（3） position of CpCo（Se2C2B10HIo） has been activated and migrated to the terminal carbon of 1-（2-furyl）- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds.
基金supported in part by the National Science Foundation(DMR-1508537).
文摘Here we describe the cation reduction and comproportionation as novel routes to synthesize electrolytes for rechargeable Mg-ion batteries.Reduction of the ammonium cation in[HNMe_(3)^(1+)][HCB_(11)H_(11)^(1-)]with metallic Mg affords the halide free carborane salt[Mg^(2+)][HCB_(11)H_(11)^(1-)]2.Comproportionation of[Mg^(2+)][HCB_(11)H_(11)^(1-)]_(2) with MgPh_(2) affords the novel monocationic electrolyte[MgPh^(1+)][HCB_(11)H_(11)^(1-)],which reversibly deposits/strips Mg with a remarkable oxidative stability of 4.6 V vs.Mg^(0/+2).
基金supported by Spanish Ministerio de Economía y Competitividad,MINEICO(CTQ2016-75150-R and“Severo Ochoa”Program for Centers of Excellence in R&D SEV-2015-0496)and Generalitat de Catalunya(2017/SGR/1720)support of the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement MSCA-IF-2016-751587+1 种基金funding by project No.PGC2018-102047-B-I00(MCIU/AEI/FEDER,UE)achieved using computers from the Supercomputing Centre of Catalonia(CESCA).
文摘Two anthracenyl-styrenyl-m-carborane triads(one non-iodinated on B,3,and one iodinated,4)were synthesized and characterized to be further linked to octavinylsilsesquioxane(OVS)via cross-metathesis,giving rise to the corresponding hybrid materials 5 and 6.The crystal structure of the non-iodinated heterosubstituted-m-carborane 3 was analyzed by X-ray diffraction.Transmission electron microscopy images of pristine OVS and hybrids 5-6 show important differences in the morphology of the particles;whereas OVS forms cubic-like particles,5-6 have a spherical shape with a broad particle-size distribution.All compounds showed similar vibronic emission spectra in solution,with maxima around 415 nm,assigned to the locally excited state(LE)emission of the anthracene moiety.The similarity with the spectra of the free anthracene(λ_(em)=420 nm)suggested that only small electronic interactions between the anthracene units have taken place,and there is no influence of the iodo or styrene groups on the absorption properties.This is in agreement with the DFT calculations,where calculated oscillator strength corresponding to the transitions from iodo orbitals to the LUMO are weak and could not be observed experimentally.Noticeable,triads 3-4 exhibited exceptional fluorescence quantum yield values of around 100%in solution,that are comparable to those determined for their precursors 1-2,demonstrating that the influence of the styrene group is negligible.Linking these m-carborane derivatives to the OVS led to a significant decrease of quantum yields to 34-45%for 5-6 in solution.Moreover,the PL behavior in the aggregate state was investigated and the spectra of all compounds were very similar,showing emission red-shift with maxima around 455-459 nm.Remarkably,quite high fluorescence quantum yields were determined for 3-4((ϕ_(F)=26-31%)and 5-6(ϕ_(F)=27-36%)in the aggregated state.These data confirm that the m-carborane platform enhances the quantum efficiency of the anthracene in solution,without losing the emission properties in the aggregate state.If this affirmation is associated to other scattered examples on other fluorophores also linked to m-carborane existing in the literature,the former conclusion is reinforced.m-Carborane enhances the fluorescence quantum yield of the free fluorophore,but does not alter the energy of the participating states in the photoluminescence in solution.
基金supported by the National Natural Science Foundation of China(22071094 and 22075123)the Jiangxi Provincial Natural Science Foundation(20213BCJ22055 and 20224ACB203004).
文摘In this study,we present the first synthesis of ferroelectric crystals where the carbon vertices of carboranes are substituted with cycloalkane groups.These crystals include 1,2-(1,3-propanediyl)-o-carborane(1)and 1,2-(1,4-hexanediyl)-o-carborane(2),both of which exhibit relatively high Curie temperatures at 328.6 K and 320.6 K.Notably,to the best of our knowledge,this represents the first instance of ferroelectric crystals derived from modifications at the carbon vertex of carborane.This discovery provides a valuable new avenue for research into novel carborane-based ferroelectrics and holds promise for advancing the broader application of ferroelectric materials.
