Er^3＋掺杂硼硅酸盐玻璃的近红外发射特性研究

利用高温熔融法合成了掺Er^3 硼硅酸盐玻璃。测量了样品的吸收光谱，由J-0理论得到了强度参数Ωλ(λ＝2，4，6)及一些相关参数；用970nm光激发测量了10-300K之间的近红外发射光谱。利用McCumber理论拟合得到了1．53μm发射的受激发射截面，并与测量得到的发射光谱线形符合较好。由受激发射截面和发射光谱得到的半高全宽分别为59和56nm。利用能级简化模型讨论了样品的红外变温发射光谱，提出了增大1．53μm发射带宽的途径。     

Yb3+敏化宽波带掺Er3+氟磷酸盐玻璃的发光性质及Judd-Ofelt理论研究

采用高温熔融法制备了一种新的Er3+/Yb3+共掺氟磷酸盐玻璃,测试和分析了其密度、吸收光谱以及荧光光谱,讨论了Er3+离子和Yb3+离子对光谱性质的影响.根据Judd-Ofelt理论计算了玻璃中Er3+离子的强度参数Ωt(t=2,4,6),分别为Ω2=4.36×10-20cm2,Ω4=1.35×10-20cm2,Ω6=0.79×10-20cm2,以及Er3+离子4I13/2能级荧光寿命τm=8.26ms.主发射峰1.53μm处半高宽(FWHM)为68nm.根据McCumber理论计算了Er3+的受激发射截面σe=8.5×10-21cm2.比较了不同玻璃基质中Er3+离子的光谱特性,结果表明:Er3+/Yb3+双掺氟磷酸盐玻璃在1.53μm附近具有较宽的半高宽和较大的受激发射截面,是一种高增益掺铒光纤放大器的理想介质材料.     

Dy~(3+)掺杂Ge-Ga-Se-KBr硫卤玻璃近红外和中红外发光特性研究

用熔融淬冷法制备了系列掺杂浓度的Dy3+∶Ge-Ga-Se-KBr硫卤玻璃样品,测试了样品的折射率、吸收光谱、近红外及中红外荧光谱。应用Judd-Ofelt理论计算了Dy3+离子的强度参数(Ωi,i=2,4,6)、自发辐射跃迁几率(A)、荧光分支比(β)和辐射寿命(τrad)等光谱参数。研究了810 nm激光泵浦下样品中红外荧光特性与掺杂浓度之间的关系,利用McCumber(MC)和Futchbauer-Ladenburg(FL)理论分别计算了常温Dy3+:6F5/2→6H9/2(2.17μm),6F11/2(6H9/2)→6H13/2(2.47)和6H13/2→6H15/2(2.86μm)中红外荧光的受激发射截面。     

Er3+掺杂Li2O-SrO-ZnO-Bi2O3玻璃中Er3+离子在1.53 μm处的荧光发射特性

采用传统的熔融法制备了Er~(3+)掺杂的新型铋酸盐玻璃(Li_2O-SrO-ZnO-Bi_2O_3,LSZB),并对其光谱性质进行了表征,分析了玻璃的拉曼光谱、吸收光谱、荧光光谱,利用Judd-Ofelt理论研究了其荧光特性。LSZB玻璃样品中Er~(3+)的~4I_(13/2)→~4I_(15/2)跃迁发射峰位于1.53 μm处,半高宽约为78 nm。样品中Er~(3+)的~4I_(13/2)能级寿命为2.848 ms,量子效率为99.93%,受激发射截面达到9.76×10~(-21)cm~2。以上结果显示,Er~(3+)掺杂LSZB玻璃有良好的光谱特性。     

新型掺铒钆硼硅酸盐玻璃的制备和光学性质的研究

用高温熔融法制备了成分为Gd2O3,SiO2,B2O3和Na2O的新型玻璃体系,探索了该玻璃体系的成玻范围,发现该系统在B2O3:20%以上,SiO2:0～50%,Gd2O3:0～30%的范围内均可形成完全透明的玻璃.在Gd2O3:30%,B2O3:60%和SiO2:60%,B2O3:30%两个组分附近时玻璃轻微失透.除此以外,在其他组分实验上没有得到玻璃.根据差热分析的数据,计算得到的玻璃析晶倾向参数β在0.32～1.76之间,说明含10%Gd2O3的钆硼硅酸盐玻璃具有较强的形成能力;利用McCumber理论计算出样品的吸收和受激发射截面,并从玻璃1.5 μm的吸收光谱出发拟合出了J-O参数,进而计算了Er3 离子各相关能级的理论振子强度、实验振子强度和自发辐射速率等参数.同时,用Er3 离子1.5 μm发射光谱的半高全宽与其峰值发射截面的乘积值对含10%Gd2O3钆硼硅酸盐玻璃1.5μm发射的增益带宽作出了表征,结果表明,含10%Gd2O3玻璃体系的FWHM×σepeak值均大于已有报道的硅酸盐、磷酸盐和锗酸盐玻璃,其中最大值和氧氟硅酸盐玻璃的相差不多.     

Er^3＋掺杂TeO2-WO3-ZnO—ZnF2玻璃的光谱性质

制备了Er^3 离子掺杂的TeO2-WO3-ZnO-ZnF2(TWZOF)玻璃，测试了样品的吸收光谱和970nmLD激发下样品中Er^3 离子的荧光光谱与荧光寿命，计算了Er^3 离子的J—O强度参数Ωt(t=2，4，6)和1．5μm波段的吸收截面与发射截面，研究了Er^3 离子1．5μm发射强度、荧光寿命和发射带宽与玻璃中ZnF2含量的关系。实验得到Er^3 离子在TWZOF玻璃中1．5μm发射的最大荧光半高宽(TwHm)为83nm；随着ZnF2含量的增加，Er^3 离子1．5μm发射强度、荧光寿命均增加。     

Cr^4＋，Nd3＋共掺的钆镓石榴石（Cr，Nd：GGG）的光谱性能与光谱参数的研究

用提拉法生长了掺铬、钕的钆镓石榴石(Cr^4 ，Nd^3 :GGG)晶体，研究了室温下的吸收光谱和荧光光谱性质，以及晶体中Cr离子浓度对Nd离子光谱性质的影响。应用Judd—ofelt理论计算了强度参数Ωt(t=2，4，6)，自发辐射跃迁几率、荧光分支比和辐射辱命等光谱参数。应用McCumber理论计算^4F3/2→^4I11/2能级跃迁的受激发射截面。结果表明：Cr^3 在300～900nm之间较强地增加了吸收截面，尤其是伴随Cr^3 →Nd^3 有效的能量转移。Cr^4 在1．06μm附近的吸收减弱了Nd离子的发射截面。     

Cr4+, Nd3+共掺的钆镓石榴石(Cr, Nd∶GGG)的光谱性能与光谱参数的研究

用提拉法生长了掺铬、钕的钆镓石榴石(Cr4+, Nd3+∶GGG)晶体, 研究了室温下的吸收光谱和荧光光谱性质, 以及晶体中Cr离子浓度对Nd离子光谱性质的影响. 应用Judd-ofelt理论计算了强度参数Ωt (t=2, 4, 6), 自发辐射跃迁几率、荧光分支比和辐射寿命等光谱参数. 应用McCumber理论计算了4F3/2→4I11/2能级跃迁的受激发射截面. 结果表明 Cr3+在300～900 nm之间较强地增加了吸收截面, 尤其是伴随Cr3+→Nd3+有效的能量转移. Cr4+在1.06 μm附近的吸收减弱了Nd离子的发射截面.     

Tm3+与Ho3+单掺杂锗酸盐玻璃的增益特性

制备了掺杂浓度分别为2．0mol％的Tm^3＋与Ho^3＋单掺的两种锗酸盐玻璃。根据McCumber理论计算了Tm^3＋离子能级^3H6←→^3F4（1．8μm）跃迁和Ho^3＋离子能级^5I8←→^5I7（2．0μm）跃迁的吸收截面和受激发射截面。同时,根据所获得的吸收截面、发射截面以及掺杂离子的浓度分别获得了Tm^3＋离子和Ho^3＋离子在两种不同锗酸盐玻璃基质中的增益截面函数,从该函数可反映出材料的粒子数反转特性。对于Tm^3＋离子掺杂的锗酸盐玻璃,其吸收截面、发射截面和增益截面的最大值大于在氟锆酸盐、氟化物和氟氧化物玻璃中;对于Ho^3＋掺杂的锗酸盐玻璃,其吸收截面、发射截面和增益截面的最大值也大于在氟锆铝酸盐玻璃。因此,Tm^3＋和Ho^3＋掺杂的两种锗酸盐玻璃在～1．8和～2．0μm波段的中红外激光器中将有潜在的应用前景。     

掺铒碲酸盐玻璃光谱特性研究

测试了样品(75-x)TeO2-xWO3-15ZnO-5La2O3-5Nb2O5(摩尔分数)-1%(质量分数)Er2O3(TWZ,x=0,4,8,12,15)和(75-y)TeO2-yB2O3-15ZnO-5La2O3-5Nb2O5(摩尔分数)-1%(质量分数)Er2O3(TBZ,y=0,4,8,12,15)玻璃的吸收光谱、荧光光谱、上转换光谱、能级寿命和热稳定性.应用J-O理论和McCumber理论分别计算了玻璃中Er3+离子光学跃迁强度参数Ωt(t=2,4,6)和受激发射截面.在975 nm激励下,该玻璃同时观察到了绿光(528和544 nm)和红光(660 nm)的上转换发光现象,分别对应于Er3+的.2Hu/2→4I15/2,4S3/2→4I15/2和 4F9/2→4I15/2跃迁.分析比较了玻璃中WO3和B2O3含量变化对光谱参数的影响.结果表明:随着WO3含量的增加,TWZ玻璃1.53μm波段荧光强度逐渐增大,上转换发光强度逐渐减弱,4I13/2能级寿命增加;随着B2O3含量的增加,TBZ玻璃1.53 μm波段荧光强度、上转换发光强度以及4I13/2能级寿命逐渐减弱.另外,TWZ和TBZ系列玻璃的热稳定性都有所提高.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.