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
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
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
A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature...A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature,these CPs manifest green phosphorescence with quantum yields of up to 60%,which is the highest value for Mn(II)CPs.CP[MnI_(2)(L)]_(n)and its structurally different solvate[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)also exhibit bright triboluminescence.Thermochromic luminescence of the designed CPs appears as reversible shifting of their emission color,when the temperature varies from 350 to 77 K and back.Moreover,[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)reversibly changes its emission properties during desolvation-solvation processes thus featuring solvatochromic luminescence.According to photophysical and EPR data,the observed phosphorescence originates from the ligand-sensitized^(4)T_(1)→^(6)A_(1)transition in Mn^(2+)ions.Enhanced robustness of the title CPs is demonstrated by retaining their emission properties after prolonged heating at 210°C.展开更多
In recent years,cyclometalated Pt(Ⅱ)complexes with a terdentate ligand have been used as prospective blue phosphorescent materials.For improving these materials further,the introduction of o-carborane is treated as a...In recent years,cyclometalated Pt(Ⅱ)complexes with a terdentate ligand have been used as prospective blue phosphorescent materials.For improving these materials further,the introduction of o-carborane is treated as an excellent strategy to promote the luminescence efficiency.A series of new materials show over 82%phosphorescence quantum yield and good stability,but they are still not fully elucidated.In this work,several different stable o-carborane cages are introduced into the traditional C,N,C-cyclometalated Pt(Ⅱ)complexes in order to explore their influence completely in contrast to the original phenyl ligand from the view of theoretical investigation.Comprehensive analyses of the geometric structure,molecular orbital and configuration information,spin-orbit coupling elements,vibrational modes,etc.have been carried out.More importantly,our theoretical model highlights that the embedded o-carborane ligands will have an impact on the photophysical properties and quantum efficiency of these Pt(Ⅱ)complexes significantly,which can provide a valuable guideline for designing and regulating several aspects of highly efficient blue phosphorescent materials.展开更多
Simultaneously achieving high luminescence quantum efficiency and narrowband emission in o-carboranyl luminophores remains a significant challenge for enhancing color purity and extending their applicability in optoel...Simultaneously achieving high luminescence quantum efficiency and narrowband emission in o-carboranyl luminophores remains a significant challenge for enhancing color purity and extending their applicability in optoelectronic materials.Herein,we report two multi-resonance induced thermally activated delayed fluorescence(MR-TADF)compounds,CB-diBNO(1)and CB-v-DABNA(2),which incorporate methyl-o-carborane units at the periphery of diboron MR cores.Both compounds exhibit characteristic narrowband MR-TADF emission with high quantum efficiency in toluene and rigid states,while displaying weak emission in THF.Compound 1 exhibits more narrowed emission spectra with bathochromic shifts compared to its phenyl-substituted counterpart,Ph-diBNO(3).Notably,its full width at half-maximum of only 11 nm ranks among the narrowest reported for boron-based MR-TADF compounds.Electrochemical analysis reveals that the incorporation of o-carborane moieties significantly stabilizes the frontier molecular orbitals of the diboron MR core compared to phenyl substitution.Theoretical studies suggest that emission quenching in THF arises from the presence of a dark lowest-energy charge transfer state,while o-carborane modification effectively suppresses low-frequency vibrations in the diboron MR-core skeleton,thereby minimizing spectral broadening.These findings highlight that diboron MR-TADF cores can serve as a promisingπ-skeleton for the design of narrowband emissive o-carboranyl luminophores.展开更多
The steric and electronic properties of A/-heterocyclic carbenes(NHCs)can be modified by the exocyclic substituents at the nitrogen atoms,by 1-3 atoms'replacements of the five-membered imidazolium skeleton and by ...The steric and electronic properties of A/-heterocyclic carbenes(NHCs)can be modified by the exocyclic substituents at the nitrogen atoms,by 1-3 atoms'replacements of the five-membered imidazolium skeleton and by the changes of the backbones.Herein,we report the usage of nido-C_(2)B_(3) carbora ne anions as the backb ones of NHCs.Stirring the mixture of sec on dary amino o-carbora nes(lb-le),triethyl orthoformate and HBF4-Et2O results in the unexpected cage-opening of o-carboranes to afford the n/do-C_(2)B_(9) carbora ne anions supported A/-heterocyclic carbene precursors(4b-4e).Deprotonation of 4b with sodium hexamethyldisilazide at-78℃ affords the/V-heterocyclic carbene ligand,which was used to form an Au(I)NHC complex(5).DFT calculations revealed a high-lying lone pair orbitals of the carbene ligands,predicting their strong o-donating abilities.展开更多
The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH...The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH_(2)-linkage have been prepared and structurally characterized for comparison.Structural analyses of 13-and 14-vertex heteroboranes as well as control experiments suggest that the facile double desilylation of 2 on silica gel can be attributed to the joint actions of several factors involving the high ring-strain of exo five-membered C_(4)Si ring,Lewis acidity of Si atom and Brønsted acidity of silica surface.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
Transmetalation of carborane-fused zirconacycles to Cu（II） induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carb...Transmetalation of carborane-fused zirconacycles to Cu（II） induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu（II） and reductive elimination is proposed.展开更多
The interactions between the new organometallic complexes,ferrocenesubstituted dithioocarborane conjugates(denoted as FcSB1,FcSB2 and FcSBCO)and hemoglobin(Hb)are investigated by electrochemistry,fluorescence and UVvi...The interactions between the new organometallic complexes,ferrocenesubstituted dithioocarborane conjugates(denoted as FcSB1,FcSB2 and FcSBCO)and hemoglobin(Hb)are investigated by electrochemistry,fluorescence and UVvis absorption spectroscopy.The results demonstrate that FcSB1,FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms,inducing the allosteric change from the R state(oxygenated conformation,relax)to T state(deoxygenated conformation,tense).The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1.Moreover,the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb.Typically,FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb.Such distinct influences are attributed to the structural features of FcSB1,FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group.Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs.展开更多
o-Carboryne （1,2-dehydro-o-carborane） is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused o...o-Carboryne （1,2-dehydro-o-carborane） is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4＋2]/[2＋2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science.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Russian Foundation for Basic Research(Project No.18-03-00300)。
文摘A series of 1D coordination polymers(CPs),[MnX_(2)(L)]_(n)(X=Cl,Br,I),made of MnX_(2)units bridged by 1,7-[Ph_(2)P(O)]_(2)-meta-carborane ligands(L)through the O-Mn-O linkages,have been designed.At ambient temperature,these CPs manifest green phosphorescence with quantum yields of up to 60%,which is the highest value for Mn(II)CPs.CP[MnI_(2)(L)]_(n)and its structurally different solvate[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)also exhibit bright triboluminescence.Thermochromic luminescence of the designed CPs appears as reversible shifting of their emission color,when the temperature varies from 350 to 77 K and back.Moreover,[MnI_(2)(L)·CH_(2)Cl_(2)]_(n)reversibly changes its emission properties during desolvation-solvation processes thus featuring solvatochromic luminescence.According to photophysical and EPR data,the observed phosphorescence originates from the ligand-sensitized^(4)T_(1)→^(6)A_(1)transition in Mn^(2+)ions.Enhanced robustness of the title CPs is demonstrated by retaining their emission properties after prolonged heating at 210°C.
基金supported by the State Key Development Program for Basic Research of China(Grant No.2013CB834801)the Natural Science Foundation of China(Grant No.21573088)+1 种基金the Young Scholar Training Program of Jilin Universitythe Open Project Funding of Beijing National Laboratory for Molecular Sciences(BNLMS).
文摘In recent years,cyclometalated Pt(Ⅱ)complexes with a terdentate ligand have been used as prospective blue phosphorescent materials.For improving these materials further,the introduction of o-carborane is treated as an excellent strategy to promote the luminescence efficiency.A series of new materials show over 82%phosphorescence quantum yield and good stability,but they are still not fully elucidated.In this work,several different stable o-carborane cages are introduced into the traditional C,N,C-cyclometalated Pt(Ⅱ)complexes in order to explore their influence completely in contrast to the original phenyl ligand from the view of theoretical investigation.Comprehensive analyses of the geometric structure,molecular orbital and configuration information,spin-orbit coupling elements,vibrational modes,etc.have been carried out.More importantly,our theoretical model highlights that the embedded o-carborane ligands will have an impact on the photophysical properties and quantum efficiency of these Pt(Ⅱ)complexes significantly,which can provide a valuable guideline for designing and regulating several aspects of highly efficient blue phosphorescent materials.
基金supported by the Basic Science Research Program funded by the Ministry of Science and ICT(MSIT)(RS-2025-00514431 for M.H.L and NRF-2021R1A2C1009191 and RS-2024-00407859 for J.J)through the National Research Foundation of Korea(NRF)support from the Technology Development Program funded by the Ministry of SMEs and Startups(MSS)(RS-2024-00508746)through the Korea Technology and Information Promotion Agency(TIPA).
文摘Simultaneously achieving high luminescence quantum efficiency and narrowband emission in o-carboranyl luminophores remains a significant challenge for enhancing color purity and extending their applicability in optoelectronic materials.Herein,we report two multi-resonance induced thermally activated delayed fluorescence(MR-TADF)compounds,CB-diBNO(1)and CB-v-DABNA(2),which incorporate methyl-o-carborane units at the periphery of diboron MR cores.Both compounds exhibit characteristic narrowband MR-TADF emission with high quantum efficiency in toluene and rigid states,while displaying weak emission in THF.Compound 1 exhibits more narrowed emission spectra with bathochromic shifts compared to its phenyl-substituted counterpart,Ph-diBNO(3).Notably,its full width at half-maximum of only 11 nm ranks among the narrowest reported for boron-based MR-TADF compounds.Electrochemical analysis reveals that the incorporation of o-carborane moieties significantly stabilizes the frontier molecular orbitals of the diboron MR core compared to phenyl substitution.Theoretical studies suggest that emission quenching in THF arises from the presence of a dark lowest-energy charge transfer state,while o-carborane modification effectively suppresses low-frequency vibrations in the diboron MR-core skeleton,thereby minimizing spectral broadening.These findings highlight that diboron MR-TADF cores can serve as a promisingπ-skeleton for the design of narrowband emissive o-carboranyl luminophores.
基金support from the National Natural Science Foundation of China(Grant No.21771048)the Natural Science Foundation of Zhejiang Provinee(Grant No.LY17B010002).
文摘The steric and electronic properties of A/-heterocyclic carbenes(NHCs)can be modified by the exocyclic substituents at the nitrogen atoms,by 1-3 atoms'replacements of the five-membered imidazolium skeleton and by the changes of the backbones.Herein,we report the usage of nido-C_(2)B_(3) carbora ne anions as the backb ones of NHCs.Stirring the mixture of sec on dary amino o-carbora nes(lb-le),triethyl orthoformate and HBF4-Et2O results in the unexpected cage-opening of o-carboranes to afford the n/do-C_(2)B_(9) carbora ne anions supported A/-heterocyclic carbene precursors(4b-4e).Deprotonation of 4b with sodium hexamethyldisilazide at-78℃ affords the/V-heterocyclic carbene ligand,which was used to form an Au(I)NHC complex(5).DFT calculations revealed a high-lying lone pair orbitals of the carbene ligands,predicting their strong o-donating abilities.
基金The work described in this paper was supported by grants from the Research Grants Council of the Hong Kong Special Administration Region(Nos.404610 and CUHK7/CRF/12G).
文摘The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH_(2)-linkage have been prepared and structurally characterized for comparison.Structural analyses of 13-and 14-vertex heteroboranes as well as control experiments suggest that the facile double desilylation of 2 on silica gel can be attributed to the joint actions of several factors involving the high ring-strain of exo five-membered C_(4)Si ring,Lewis acidity of Si atom and Brønsted acidity of silica surface.
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 (404011)the National Natural Science Foundation of China (21372245 to QIU ZaoZao)
文摘Transmetalation of carborane-fused zirconacycles to Cu（II） induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu（II） and reductive elimination is proposed.
基金supported by the National Basic Research Program of China(2010CB732404,2010CB923303)the National Natural Science Foundation of China(21175020,90713023,20925104)+4 种基金the Project of High Technology Research and Development Program of China(2007AA022007)Gongdong Province(2011B090400357)the Natural Science Foundation of Jiangsu Province(BK2008149,BK2010052)C.W.acknowledges the Fundamental Research Funds for the Central Universities(ZYGX2011J099)the support by the Open Research Fund of State Key Laboratory of Bioelectronics,Southeast University(2011E09)
文摘The interactions between the new organometallic complexes,ferrocenesubstituted dithioocarborane conjugates(denoted as FcSB1,FcSB2 and FcSBCO)and hemoglobin(Hb)are investigated by electrochemistry,fluorescence and UVvis absorption spectroscopy.The results demonstrate that FcSB1,FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms,inducing the allosteric change from the R state(oxygenated conformation,relax)to T state(deoxygenated conformation,tense).The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1.Moreover,the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb.Typically,FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb.Such distinct influences are attributed to the structural features of FcSB1,FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group.Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs.
文摘o-Carboryne （1,2-dehydro-o-carborane） is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. Diels-Alder reaction of o-carboryne with furans gave a series of carborane-fused oxanorbornenes in moderate to high yields using 1-OTf-1,2-C_2B_10H_11 as carboryne precursor. The resultant cycloadducts can undergo hydrogenation, cyclic oxidation, bromination, [4＋2]/[2＋2] cycloaddition and nucleophilic ring opening reaction to afford a variety of highly functionalized carboranes that may find applications as useful basic units in medicine and materials science.
