溶胶-凝胶法制备YAl3(BO3)4粉末

使用溶胶-凝胶法、XRD与SEM等方法,研究了YAl3(BO3)4的合成参数.相对于固相合成YAl3(BO3)4需要温度1200 ℃才能形成纯相,溶胶-凝胶法当灼烧温度为900 ℃时,YAl3(BO3)4主相已经形成,当温度升至1100 ℃,可制得纯相,其粒径大约为1 μm.但其中存在晶粒大小不均问题,需进一步研究.     

CO(NH2)2-H3BO3-H2O体系相平衡研究

农作物不仅需要吸收C、H、O、N、P、K、Ca、Mg等营养元素,而且还需要吸收B、Mn、Zn等营养元素,以维持它们正常生长的需要.尿素是一种含氮量很高(46.60%)、性能很好的氮肥,而硼化合物又是一种很重要的微量元素肥料.因此,研究尿素与硼化合物间的相互作用,以得到既含氮又含硼的一种化合物,是一种很有意义的工作。目前,国外已开展了尿素与硼酸间相互作用的研究工作.研究结果表明,在一定条     

B_n(BO)_n~(2-)、CB_(n-1)(BO)_n~-和C_2B_(n-2)(BO)_n(n=5~12):类似于笼状B_nH_n~(2-)、CB_(n-1)H_n~-和C_2B_(n-2)H_n的硼氧团簇

笼状硼氢化合物BnHn2-、CBn-1Hn-和C2Bn-2Hn(n=5~12)含n个顶点和(n+1)对骨架电子,具有典型的三维芳香性、高的芳香化能和类似于苯的化学反应性.2005年以来,在研究B-O二元团簇的过程中,我们首次提出硼的硼羰基化合物(boron boronyls)和碳的硼羰基化合物(carbon boronyls)的概念,探讨了Bn(BO)m0/-1/-2(n=1~2,m=2~4)及Cn(BO)n(n=3~7)系列化合物的几何结构和电子性质.基于高分辨光电子能谱实验和密度泛函理论分析,确认线性B(BO)20/-1及三角形B(BO)30/-1新颖结构,首次发现线性D∞h B2(BO)22-离子含有B≡B三重键.理论和实验结合研究表明,BO与H具有等瓣相似性,BO自由基具有类似于CN的化学行为.在此基础上,本文用BO基团取代BnHn2-、CBn-1Hn-及C2Bn-2Hn(n=5~12)中的H原子,形成Bn(BO)n2-、CBn-1(BO)n-及C2Bn-2(BO)n(n=5~12)系列硼氧化物,对其几何和电子结构、稳定性和芳香性进行密度泛函B3LYP/6-311+G(3df)理论研究.图1给出n=1...     

C3N6H6(H3BO3)2的合成及晶体结构

以三聚氰胺和硼酸为原料在水溶液中反应合成出了一种新的BCN化合物先驱体C3N6H6(H3BO3)2。XRD表征结果表明三聚氰胺和硼酸的最佳配比为1∶3(物质的量比)。用单晶X-射线衍射分析法测定了该化合物的晶体结构。该化合物属单斜晶系,空间群为P21/C,晶胞参数为a=0.3597(7)nm,b=2.0105(4)nm,c=1.4112(3)nm,α=90,°β=92.07(3),°γ=90,°V=1.0199(3)nm3,Z=4,D c=1.627g.cm-3,μ(MoKα)=0.144mm-1,F(000)=520。晶体结构经全矩阵最小二乘法修正,最终可靠因子R1=0.0519,wR2=0.1361。该化合物是由C3N6H6分子和H3BO3分子通过氢键加合组装形成的三维超分子结构化合物。     

Dy3+在Ba3La(BO3)3 中的光致发光

研究了Ba3La(BO3)3 基质中Dy3 的光致发光特性; 探讨了RE3 的电荷半径比(z/r)和Ce3 , Dy3 含量对Dy3 发光强度及发光颜色的影响; 分析了Ba3La(BO3)3 中Ce3 对Dy3 发光的敏化作用; 确定了Dy3 的 4F9/2→6H15/2及4F9/2→6H13/2跃迁发射的浓度猝灭机制均为电偶极-电四极相互作用.     

Crystal and molecular structures of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones

An X-ray study of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones is reported. The bond lengths inside the H ring are equalized due to the classical N-H...O hydrogen bond between the carbonyl oxygen and the amino group. In the 4-(2′-hydroxyethyl)amino-pent-3-en-2-one crystal, due to the classical N-H...O bonds, infinite zigzag chains are formed along the 0b axis and arranged into a layered structure due to the weak C-H...O interactions. In (±)-4-(2′-hydroxypropyl)aminopent-3-en-2-one crystal, however, centrosymmetric dimers are formed, which are then linked by weak C-H...O intermolecular interactions to form a layered structure along the a0b plane.     

BO基杂配位铁羰基化合物Fe_2(BO)_2(CO)_n(n=9,5)的配位特性研究

含硼的双原子配体(如BO、BF等)稳定性差,有关BO基配位取代金属羰基化合物的实验研究和理论研究均较少,对配位过饱和及高度不饱和过渡金属配位体系的配位研究还鲜见报道.本文采用两种密度泛函方法 B3LYP和BP86对BO基杂配位的过饱和及高度不饱和铁羰基化合物Fe2(BO)2(CO)n(n=9,5)的配位特性进行了研究.研究结果表明,在配位过饱和Fe2(BO)2(CO)9中,两个Fe原子间距较大,没有明显直接成键作用.其低能构型都是桥连结构且更倾向于CO桥而不是BO桥,BO基多以端配位的形式出现;由于其体系配位过饱和的特征,优化的低能构型中出现了BO基耦合于端位CO基的配位结构29-6S和29-8S.在配位高度不饱和Fe2(BO)2(CO)5体系中,所有低能构型也都是桥连结构但倾向于BO桥而不是CO桥,显现BO基中氧原子的碱性比CO基中氧原子的碱性更强;由于其配位高度不饱和,构型25-1S、25-4T和25-5T中存在两个3-电子给体桥?2-μ-BO配位;25-2T、25-3T和25-6T中存在两个"首尾相连"的3-电子给体"–B–O–"桥;结构25-1T中出现了由两个BO配体耦合形成的4-电子给体反式双硼双氧(B2O2)配体.无论从单羰基离解能还是单核离解能来看,Fe2(BO)2(CO)5的热力学稳定性都远比Fe2(BO)2(CO)9高,可望是一个潜在的合成目标.     

Covalent Bonding in Au(BO) 2 − and Au(BS) 2 −

We perform in this work a comprehensive first-principles investigation on the geometric and electronic structures of Au(BO) ₂ ^? and Au(BS) ₂ ^? which are valent isoelectronic to the well-known Au(CN) ₂ ^? monoanion. Au(BO) ₂ ^? and Au(BS) ₂ ^? complexes prove to possess linear ground-state structures similar to Au(CN) ₂ ^? and the BO^? and BS^? ligands in them are found to be coordinated terminally via boron atoms to gold centers which are weakly negatively charged. Au–B bonds in Au(BO) ₂ ^? and Au(BS) ₂ ^? appear to have higher Wiberg bond indices (0.79 and 0.80) and more covalent components (60 and 53 %) than the corresponding values of Au–C interaction in Au(CN) ₂ ^? (0.67 and 39 %, respectively) at the same theoretical levels. Their Au–B bifurcation values of the electronic localization function also turn out to be higher than Au–C. These results strongly suggest that the Au–B bonds in Au(BO) ₂ ^? and Au(BS) ₂ ^? with multiple-bond character possess stronger covalent characters than Au–C in Au(CN) ₂ ^? .     

2-Polyfluoroalkylchromones. 11. Synthesis and structures of 5-hydroxy-3-(2-hydroxyaryl)-5-polyfluoroalkyl-Δ2-pyrazolines and 3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles

The reaction of 2-hydroxy-2-polyfluoroalkylchroman-4-ones with hydrazine affords 5-hydroxy-3-(2-hydroxyaryl)-5-polyfluoroalkyl-²-pyrazolines, whereas 2-polyfluoroalkylchromones under similar conditions produce 3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles. 5-(2-Hydroxyaryl)-1-methyl-3-polyfluoroalkylpyrazoles were synthesized in the reaction with methylhydrazine, and the reaction with phenylhydrazine afforded regioisomeric 3(5)-(2-hydroxyphenyl)-1-phenyl-5(3)-polyfluoroalkylpyrazoles.     

LaAl3(BO3)4的合成及其晶体结构的研究

在研究LnAl3(BO3)(Ln=稀土元素，Y）的合成及发光特性过程中，发现镧铝硼酸盐LaAl3(BO3)4具有一种新的晶体结构。本文用助熔剂法合成了LnAl3(BO3)4(Ln=Gd,La)单晶样品，LaAl3(BO3)4为薄板状，而GdAl3(BO3)4为六方的棒状，用TREOR90程序对LaAl3(BO3)4粉末样品的X射线衍射数据进行了指标化，结果为：LaAl3(BO3)4属正交晶系，晶胞参数为a=0.93586(4)nm,b=0.79904(3)nm,c=0.40626(6)nm,V=0.34595nm^3，在1000℃空气环境下，用硝酸盐热分解法合成了单相LnAl3(BO3)4:E3 （Ln=Gd,La)荧光粉并研究了其发光特性，结果表明：LnAl3(BO3)4:Eu^3 (Ln=Gd,La)是非常有前途的等离子显示器用荧光粉。     

Ru(bipy)_3~(2+)-CO_3~(2-)-SO_3~(2-)-KClO_3体系化学发光法测定空气中的二氧化硫

提出了 Ru(bipy) 2 +3 - CO2 -3 - SO2 -3 - KCl O3 体系化学发光法测定溶液中亚硫酸盐的方法。SO2 -3 浓度与化学发光强度在 1 .0× 1 0 - 7～ 1 .0× 1 0 - 4mol/L 范围内成正比 ,检出限为 8.76× 1 0 - 8mol/L,对 1 .0× 1 0 - 4mol/L SO2 - 3 溶液 6次测定的相对标准偏差为 2 .9%。该法用三乙醇胺作为吸收液 ,成功地用于测定空气中二氧化硫的含量 ,结果满意。     

Synthesis of 3-(2-(4-Chlorophenylimino)-3-(4-chlorophenyl)-2,3-dihydrothiazol-4-yl)-2 h-Chromen-2-one via Multicomponent Approach

A simple and highly efficient one-pot, three-component synthesis of 3-(2-(4-chlorophenylimino)-3-(4-chlorophenyl)-2,3-dihydrothiazol-4-yl)-2H-chromen-2-ones has been reported by the reaction of 3-(2-bromoacetyl)-2H-chromen-2-one, primary amines, and phenyl isothiocyanates in presence of dimethylformamide as a solvent. The structures of newly synthesized compounds were confirmed by their analytical and spectral data.     

Crystal Structure and Spectra Characters of 2-Benzoly-3-(4-(1,2,4-triazole)-5-anilino-thiophene and 2-(4-Methyl-benzoly)-3-(4- chlrolphenyl)-3-(1,2,4-triazole)-5-anilino-thiophene

Triazole derivatives are widely studied, because they represent the largest group of modern fungicides and are widely used both in human and veterinary therapy and in agriculture. We synthesized the title compound in which the thiophene ring was substituted by a 1,2,4-triazole group, a phenacyl group, a phenylaminol group and a benzene ring.     

硼酸盐水溶液热力学研究II: H3BO3-LB(OH)4-LiCl-MgCl2体系

在278.15～318.15K下, 测定了无液电池(A), Pt, H2│B(OH)3(m1),LiB(OH)4(m)2, LiCl(m3), MgCl2(m4)│AgCl, Ag和电池(B), Pt, H2│B(OH)3(m1), LiB(OH)4(m2), MgCl2(m4)│AgCl, Ag的电动势。利用Debye-Huckel外推法和多项式拟合法确定了硼酸镁离子对[MgB(OH)4^+缔合常数pKt, 并得到了经验方程pKt=A1+A2/T+A3T以及缔合过程的其他各标准热力学量, 同时指出缔合熵是形成[MgB(OH)4^+]离子对的推动力。     

硼酸盐水溶液热力学研究II: H3BO3-LB(OH)4-LiCl-MgCl2体系

在278.15～318.15K下, 测定了无液电池(A), Pt, H2│B(OH)3(m1),LiB(OH)4(m)2, LiCl(m3), MgCl2(m4)│AgCl, Ag和电池(B), Pt, H2│B(OH)3(m1), LiB(OH)4(m2), MgCl2(m4)│AgCl, Ag的电动势。利用Debye-Huckel外推法和多项式拟合法确定了硼酸镁离子对[MgB(OH)4^+缔合常数pKt, 并得到了经验方程pKt=A1+A2/T+A3T以及缔合过程的其他各标准热力学量, 同时指出缔合熵是形成[MgB(OH)4^+]离子对的推动力。     

Eu2+在M3La3(BO3)4(M=Ca,Sr,Ba)中的发光性质

本文研究了Eu²⁺离子在M_yAl_xBO_y+3/2(1+x)(M=Ca,Sr,Ba)基质中的发光性质及磷和卤素对发光的影响。 采用以H₂和N₂混合气体为还原气氛在高温下进行固相反应的方法合成了一系列磷光体。发现,在CaAl_xBO_2.5+3/2x基质中,当X在0.5～2的范围内时及在Sr_yAl₂BO_{4 6+}基质中,当y在2～6的范围时掺入的Eu³⁺不能被H₂还原为Eu²⁺。其他Eu²⁺激活的磷光体一般都产生f～d跃迁的宽带发射,发射峰的波长随着基质组成的不同可在400～600nm的区间的变化。     

Crystal Structure of Methyl 3- (2-chlorophenyl )-3- (5, 5-dimethyl-3-hydroxy-2-cyclohexene- 1-one-2-yl) propionate

1INTRODUCTIONInorganicsolidsupportsascatalystshavebeenwellstudied,becauseoftheirap-plicationsinorganicsynthese('~".Recently,wehavereportedtheKnoevenagelcon-densationcatalysedbyKF-Al,O,['i.Inthispaper,wediscussedthecrystalstruc-tureofthetitlecomPoundsynthesizedbythereactionof2-chlorobenzaldehydey5,5-dimethyl-1,3-cyclohexanedioneandisopropylidenemalonateinmethanolcatalyzedbyKF-Alzo,'Inordertoconfirmthestructureofthetitlecompound,theX-raycrys-tallOgraphicstudywascarriedout.2EXPER1MEN…     

SYNTHESIS OF 3-(2-QUINOLYL)TROPOLONES

3-Acetyltropolone was reacted with 2-aminobenzaldehydes to afford 3-(2-quinolyl)tropolones.2-Acetyl-7-methylaminotropone and 2-acetyl-7-ethylamino-tropone were respectively reacted with 2-aminobenzaldehydes to give the corres-ponding 2-(2-quinolyl)-7-methylaminotropones and 2-(2-quinolyl)-7-ethylaminotro-pones,which after treatment with sodium hydroxide solution also afforded 3-(2-quinolyl)tropolones.     

(2R，3R)-和(2S，3S)-2-(4-羟基-3-甲氧基)-3-羟甲基-1，4-苯并二氧六环-6-醛的对映选择性合成

1,4-苯并二氧六环木脂素类天然产物多数具有增加胆碱乙酰化酶和抗肝毒等活性 ,其活性主要源于 1 ,4-苯并二氧六环官能团 [1] . 1 ,4-苯并二氧六环木脂素的消旋全合成已有报道 [2 ] ,但其不对称合成还是空白[3] .我们发展了一条对映选择性合成 1 ,4-苯并二氧六环木脂素的简捷有效的路线 .基于前面的工作 [4 ] ,我们发现 1 ,4-苯并二氧六环醛类衍生物是合成此类天然产物的关键中间体 ,选择 2 - (4-羟基- 3-甲氧基 ) - 3-羟甲基 - 1 ,4-苯并二氧六环 - 6-醛 (1 )作为目标分子 ,其合成路线如下 :Reagents and conditions:( ) Me OH,H2 SO4,9…