• 
    

    
    

      99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

      雙(1, 2-二氰基二硫烯)合銅(II)-二氟芐基三苯基季鏻鹽的合成、晶體結(jié)構(gòu)和磁學(xué)性能

      2016-05-12 00:58:38滿麗敏王冰戊鄭萬琦廖曉嵐鄭曉耿楊卓鴻倪春林
      化學(xué)研究 2016年2期
      關(guān)鍵詞:磁學(xué)芐基苯環(huán)

      滿麗敏,王冰戊,鄭萬琦,廖曉嵐,鄭曉耿,楊卓鴻,倪春林

      (華南農(nóng)業(yè)大學(xué) 材料與能源學(xué)院,生物材料研究所, 廣東 廣州 510642)

      ?

      雙(1, 2-二氰基二硫烯)合銅(II)-二氟芐基三苯基季鏻鹽的合成、晶體結(jié)構(gòu)和磁學(xué)性能

      滿麗敏,王冰戊,鄭萬琦,廖曉嵐,鄭曉耿,楊卓鴻,倪春林*

      (華南農(nóng)業(yè)大學(xué) 材料與能源學(xué)院,生物材料研究所, 廣東 廣州 510642)

      摘要:以1,2-二氰基二硫烯二鈉鹽(Na2mnt), CuCl2·2H2O和溴化3,5-二氟芐基三苯基季鏻鹽([BiFBzTPP]Br)為原料,成功合成了1種新的含1, 2-二氰基二硫烯銅配陰離子的取代芐基三苯基復(fù)合季鏻鹽[BiFBzTPP]2[Cu(mnt)2]. 并采用元素分析、紅外光譜、紫外-可見光譜和單晶X射線衍射對(duì)所合成的季鏻鹽進(jìn)行了結(jié)構(gòu)表征. 結(jié)果表明, 季鏻鹽為單斜晶系,P2(1)/n空間群,晶胞參數(shù)為a = 0.994 9(1) nm, b = 0.154 2(1) nm, c = 0.186 6(1) nm, α = 90°, β = 100.977(3)°, γ = 90°, V = 2.680 1(4) nm3, Z = 2, R1 =0.049 9, wR2 = 0.113 8. 該季鏻鹽的分子結(jié)構(gòu)單元由2個(gè)[BiFBzTPP]+陽離子和1個(gè)[Cu(mnt)2](2-)陰離子組成. 其結(jié)構(gòu)特點(diǎn)是季鏻鹽中的陽離子和陰離子通過C-H…S, C-H…N氫鍵和 p(N)…π 堆積作用相連接. 變溫磁化率測(cè)試顯示,季鏻鹽隨著溫度的降低呈現(xiàn)弱的鐵磁耦合特性.

      關(guān)鍵詞:雙(1,2-二氰基二硫烯)銅;取代芐基三苯基季鏻鹽;晶體結(jié)構(gòu);磁學(xué)性能

      二硫烯過渡金屬配陰離子配合物具有非常好的光電性質(zhì),廣泛用于構(gòu)筑分子導(dǎo)體和分子磁體等無機(jī)-有機(jī)雜化材料[1-4]. 在這一類材料中,有機(jī)陽離子的構(gòu)型和大小可以調(diào)控二硫烯過渡金屬配陰離子的重疊模式和堆積方式,從而進(jìn)一步影響材料的物理性質(zhì)[4]. 自1996年發(fā)現(xiàn)NH4[Ni(mnt)2·H2O](mnt2-為馬來二氰基二硫烯)在4.5 K以下表現(xiàn)出鐵磁有序以來[5],以M(mnt)2(M = Ni, Pd, Pt)為基礎(chǔ)的雜化材料因其新穎的磁學(xué)性質(zhì)越來越引起人們的關(guān)注[3, 6-11]. 研究表明,對(duì)于含[M(mnt)2 -(M = Ni, Pd, Pt; mnt = 1, 2-二氰基二硫烯) 配陰離子的雜化材料,取代芐基吡啶或異喹啉季銨鹽陽離子有利于配陰離子形成一維的柱,其中的金屬離子則形成了一維的磁鏈,并表現(xiàn)出低溫鐵磁耦合、自旋-派爾斯轉(zhuǎn)變、自旋間隙等多變的磁學(xué)性能[6, 9-13]. 近些年來,我們課題組將取代芐基三苯基鏻陽離子([RBzTPP]+)引入含[M(mnt)2]n-(M 為 Ni(III), Cu(II),n= 1或2)體系,制備了一系列的雜化材料,比較系統(tǒng)地研究了它們的晶體結(jié)構(gòu)、弱相互作用、磁學(xué)性能以及陽離子中的取代基對(duì)結(jié)構(gòu)和性質(zhì)的影響[14-17]. 本工作以1,2-二氰基二硫烯二鈉鹽(Na2mnt), CuCl2·2H2O和溴化3,5-二氟芐基三苯基季鏻鹽([BiFBzTPP]Br)為原料,合成了1種新的含1,2-二氰基二硫烯銅配陰離子的取代芐基三苯基復(fù)合季鏻鹽[BiFBzTPP]2[Cu(mnt)2],并采用元素分析、紅外光譜、紫外-可見光譜和單晶X射線衍射對(duì)所合成的季鏻鹽進(jìn)行了結(jié)構(gòu)表征,分析了季鏻鹽中的陽離子和陰離子之間的氫鍵和 p(N)…π 堆積作用,研究了季鏻鹽變溫磁學(xué)性能.

      1實(shí)驗(yàn)部分

      1.1原料與儀器

      二水氯化銅、3,5-二氟芐溴、三苯基膦、乙腈和異丙醇等均為分析純,沒有進(jìn)一步純化,直接使用. 1, 2-二氰基二硫烯二鈉鹽(Na2mnt)、溴化3,5-二氟芐基三苯基季鏻鹽([BiFBzTPP]Br)均按文獻(xiàn)[18- 19]方法合成. 標(biāo)題季鏻鹽的C、H、N含量用德國(guó)Elemental Vario III型元素分析儀測(cè)定,紅外光譜利用KBr壓片法由美國(guó)Nicolet FT-IR紅外光譜儀測(cè)定,紫外-可見光譜由日本UV-Vis 4000型紫外-可見分光光計(jì)測(cè)定(乙腈作溶劑),晶體數(shù)據(jù)用德國(guó)Bruker Smart CCD型X射線單晶衍射分析儀收集(Mo Kα光源λ= 0.071 073 nm).

      1.2季鏻鹽的合成

      稱取 0.38 g(2.0 mmol)Na2mnt于 150 mL 燒杯中,用10 mL甲醇溶解,再稱取 0.18 g(1.0 mmol)的 CuCl2·2H2O,溶于 10 mL 甲醇后,攪拌滴入前者的 Na2mnt 溶液中,溶液變成紅棕色. 然后攪拌條件下緩慢滴加20 mL 含0.94 g(2.0 mmol)[BiFBzTPP]Br 的甲醇溶液,有紅棕色沉淀生成. 反應(yīng) 30 min 后, 進(jìn)行抽濾, 并將沉淀用甲醇洗滌 3~5 次,然后真空干燥,后用乙腈和異丙醇(體積比 2∶1)混合溶劑進(jìn)行重結(jié)晶,收集到深紅色小顆粒晶體0.92 g,產(chǎn)率為 82.1%. 取少量深紅色固體,用乙腈和異丙醇(體積比 1∶1)混合溶劑溶解,室溫下自然揮發(fā),3 w后得紅棕色晶體.

      1.3季鏻鹽的單晶結(jié)構(gòu)測(cè)定

      選取大小合適的紅棕色晶體, 置于Bruker SMART CCD 單晶衍射儀上, 用經(jīng)石墨單色器單色化的Mo Kα射線 (λ = 0.071 073 nm)作為光源,在 293 K 下以φ-ω掃描方式收集到獨(dú)立衍射點(diǎn)4 997 個(gè). 晶體結(jié)構(gòu)采用SHELXS-97程序以直接法解出[20-21]. 用最小二乘法精修后的一致性殘差因子為R1= 0.049 9,wR2= 0.113 8. 最后的差值電子云密度圖中殘余電子密度的最高峰為 4.50 × 102 nm-3,最低峰為 -4.20 × 102 nm-3. 季鏻鹽的晶體學(xué)數(shù)據(jù)見表1,CCDC: 1431389.

      表1 [BiFBzTPP]2[Cu(mnt)2]的晶體學(xué)數(shù)據(jù)

      續(xù)表1

      2結(jié)果與討論

      2.1季鏻鹽的元素分析

      季鏻鹽的元素分析實(shí)驗(yàn)測(cè)定值(%)為:C, 61.29;H, 4.05;N, 4.86. 由化學(xué)式[BiFBzTPP]2[Cu(mnt)2](C58H40F4N4S4P2Cu) 的計(jì)算值(%)為:C, 61.50;H, 3.92;N, 4.95. 實(shí)測(cè)值與計(jì)算值吻合.

      2.2季鏻鹽的紅外光譜和紫外-可見光譜

      季鏻鹽紅外光譜中3 056 cm-1和2 935,2 897 cm-1分別為苯環(huán)上C-H伸縮振動(dòng)和-CH2-中的C-H伸縮振動(dòng). 2 196 cm-1的強(qiáng)吸收帶可歸屬為mnt配體中C≡N的伸縮振動(dòng)[22]. 苯環(huán)中C=C的伸縮振動(dòng)出現(xiàn)在1 581和1 461 cm-1處,而mnt中C=C的伸縮振動(dòng)出現(xiàn)在1 437 cm-1處[22];1 111和996 cm-1處的吸收帶分別歸屬于陽離子中C-F和C-P的伸縮振動(dòng); 877, 735 和686 cm-1處的吸收帶歸屬于陽離子中取代苯環(huán)C-H的變形振動(dòng)(見圖1).

      圖1 [BiFBzTPP]2[Cu(mnt)2]的紅外光譜圖Fig.1 FT-IR spectrum of [BiFBzTPP]2[Cu(mnt)2]

      季鏻鹽的紫外-可見光譜中 276, 319,368 和 480 nm處的吸收峰分別為L(zhǎng)→L*,L(σ)→Cu, L(π)→Cu和 M→L 躍遷所致(見圖2),與含 [Cu(mnt)2]2-無機(jī)配陰離子的其他季鏻鹽的電子光譜基本一致[23].

      圖2 [BiFBzTPP]2[Cu(mnt)2]紫外-可見吸收光譜Fig.2 UV-Vis absorption spectrum of [BiFBzTPP]2[Cu(mnt)2]

      2.3季鏻鹽的晶體結(jié)構(gòu)

      如圖3所示,季鏻鹽 [BiFBzTPP]2[Cu(mnt)2] 的一個(gè)不對(duì)稱的單胞中由1個(gè) [BiFBzTPP]+陽離子和 0.5 個(gè) [Cu(mnt)2]2-陰離子組成. 在[Cu(mnt)2]2-陰離子中,1 個(gè) Cu(II) 離子與2個(gè)mnt2-配體中 4 個(gè)硫原子配位,并呈現(xiàn)出平面正方形的幾何構(gòu)型,2個(gè)氰基輕微地偏離 Cu(1)S(1)C(2)C(3)S(2) 平面,其中 N(1) 和 N(2) 的偏離值分別為 -0.011 7 和 0.028 4 nm; Cu(1)-S(1) 和 Cu(1)-S(2) 的鍵長(zhǎng)分別為0.226 6 和 0.227 0 nm,S(1)-Cu(1)-S(2) 的鍵角為 91.12°;表2中所列的主要的鍵長(zhǎng)和鍵角與文獻(xiàn)報(bào)道的含 [Cu(mnt)2]2-無機(jī)配陰離子的其它季鏻鹽的基本一致[15, 23]. [Cu(mnt)2]2-陰離子之間沒有發(fā)現(xiàn)明顯的相互作用,最短的Cu…Cu的距離分別為0.948 6 nm. 在[BiFBzTPP]+陽離子中,4個(gè)苯環(huán)向由C(10)-C(11)-P(1)所確定的參考平面扭曲,C(10)-C(11)-P(1)平面與4個(gè)苯環(huán)平面之間的夾角分別為86.3°[C(5)-C(10)苯環(huán)],79.0°[C(12)-C(17)苯環(huán)],16.1° [C(18)-C(23)苯環(huán)]和83.0°[C(24)-C(29)苯環(huán)].

      所合成新季鏻鹽的結(jié)構(gòu)特點(diǎn)是[BiFBzTPP]+陽離子和[Cu(mnt)2]2-陰離子存在 3 種相互作用:1)陰離子中的N(1)原子與陽離子中的C(12)-C(17)苯環(huán)形成的p(N)…π堆積作用[24],其中N(1)原子到C(12)-C(17)苯環(huán)中心的距離為0.347 7 nm, 如圖4所示; 2)陽離子中的C(11)-H(11A)與陰離子中的S(1)原子形成的C-H…S氫鍵[25],其中C(11)…S(1)和H(11A)…S(1)的距離分別為 0.368 7和 0.287 0 nm,鍵角為142.0°(圖5). 3)陽離子中的C(5)-H(5)與陰離子中的N(2)原子形成的C-H…N氫鍵[25],其中C(5)…N(2)和H(5)…N(2)的距離分別為 0.336 0和 0.256 0 nm,鍵角為144.0°. 正是由于這些陽離子-陰離子的相互作用才導(dǎo)致季鏻鹽形成二維的網(wǎng)狀結(jié)構(gòu)(圖6).

      圖3 季鏻鹽[BiFBzTPP]2[Cu(mnt)2]的結(jié)構(gòu)式Fig.3 Molecular structure of [BiFBzTPP]2[Cu(mnt)2]

      BondLength/nmBondLength/nmBondLength/nmCu(1)-S(1)0.2266(1)N(2)-C(4)0.1136(6)C(9)-C(10)0.1384(8)Cu(1)-S(2)0.2270(1)C(5)-C(6)0.1393(7)P(1)-C(11)0.1814(4)F(1)-C(6)0.1421(6)C(6)-C(7)0.1371(11)P(1)-C(17)0.1783(3)F(2)-C(8)0.1519(8)C(7)-C(8)0.1339(11)P(1)-C(23)0.1794(3)N(1)-C(1)0.1138(5)C(8)-C(9)0.1375(9)P(1)-C(29)0.1789(3)BondAngle/(°)BondAngle/(°)S(1)-Cu(1)-S(2)91.12(3)C(17)-P(1)-C(29)114.6(3)Cu(1)-S(1)-C(2)101.29(11)C(23)-P(1)-C(29)109.7(3)Cu(1)-S(2)-C(3)100.92(11)F(1)-C(6)-C(5)111.6(4)C(11)-P(1)-C(23)109.24(18)F(1)-C(6)-C(7)110.9(5)C(11)-P(1)-C(17)107.62(18)F(2)-C(8)-C(7)119.2(5)C(11)-P(1)-C(29)110.78(18)F(2)-C(8)-C(9)120.6(5)C(17)-P(1)-C(23)109.01(14)P(1)-C(11)-C(10)114.7(3)

      圖4 [BiFBzTPP]+陽離子和[Cu(mnt)2]2-陰離子之間的p(N)…堆積作用Fig.4 p(N)… stacking interactions between [BiFBzTPP]+ cations and [Cu(mnt)2]2- anion

      圖5 [BiFBzTPP]+陽離子和[Cu(mnt)2]2-陰離子之間的氫鍵作用Fig.5 Hydrogen bonding between the [BiFBzTPP]+ cations and [Cu(mnt)2]2- anion

      圖6 季鏻鹽[BiFBzTPP]2[Cu(mnt)2]的二維的網(wǎng)狀結(jié)構(gòu)Fig.6 2D network structure of [BiFBzTPP]2[Cu(mnt)2]

      2.4季鏻鹽的磁學(xué)性能

      季鏻鹽的變溫磁化率是采用粉晶樣品在 2 000 Oe 場(chǎng)強(qiáng)下,2~300 K 溫度范圍內(nèi)測(cè)定,其χm和χmT對(duì)T曲線如圖7所示. 當(dāng)T= 300 K 時(shí),χmT值為0.374 cm3·K·mol-1,接近于沒有耦合作用的單個(gè)Cu離子(S= 1/2,g= 2)所對(duì)應(yīng)的值 (0.375 cm3·K·mol-1). 隨著溫度的降低,季鏻鹽的χmT值開始緩慢減少,大約235.6 K時(shí),χmT值為 0.362 cm3·K·mol-1. 隨著溫度繼續(xù)降低,季鏻鹽的χmT值又開始緩慢增加,2 K 時(shí)達(dá)到0.397 cm3·K·mol-1. 用Curie-Weiss 定律χm-1=(T-θ)/C對(duì)季鏻鹽的2~300 K溫度范圍的實(shí)驗(yàn)數(shù)據(jù)進(jìn)行最小平方擬合,得到的χm-1對(duì)T曲線為一條直線(圖8). 最佳擬合參數(shù)Weiss常數(shù)θ= 1.91 K,Curie常數(shù)C= 0.363 cm3·K·mol-1. Weiss 常數(shù)θ為正值表明隨著溫度的降低,季鏻鹽在2~300 K溫度范圍總體上存在弱的鐵磁耦合作用[26].

      圖7 季鏻鹽[BiFBzTPP]2[Cu(mnt)2]的χm-T和χmT-T曲線Fig.7 χm-T and χmT-T curves of [BiFBzTPP]2[Cu(mnt)2]

      圖8 季鏻鹽[BiFBzTPP]2[Cu(mnt)2]的χm-1-T圖Fig.8 χm-1-T graph of [BiFBzTPP]2[Cu(mnt)2]

      3結(jié)論

      合成了1種新的含1, 2-二氰基二硫烯銅配陰離子的取代芐基三苯基復(fù)合季鏻鹽[BiFBzTPP]2[Cu(mnt)2], 由元素分析、紅外光譜、紫外-可見光譜和單晶X射線衍射研究表明,所制備季鏻鹽的一個(gè)不對(duì)稱的單胞中由1個(gè) [BiFBzTPP]+陽離子和 0.5 個(gè) [Cu(mnt)2]2-陰離子組成,其中的陽離子和陰離子通過C-H…S, C-H…N氫鍵和 p(N)…π 堆積作用相連接,隨著溫度的降低,季鏻鹽呈現(xiàn)弱的鐵磁耦合性質(zhì).

      參考文獻(xiàn):

      [1] AKUTAGAWA T, NAKAMURA T. [Ni(dmit)2] salts with supramolecular cation structure [J]. Coord Chem Rev, 2000, 189(1): 297-311.

      [2] CASSOUX P. Molecular superconductors derived from bis-dithiolate metal complexes [J]. Coord Chem Rev, 1999, 185/186(5): 213-232.

      [3] ROBERTSON N, CRONIN L. Metal bis-1, 2-dithiolene complexes in conducting or magnetic crystalline assemblies [J]. Coord Chem Rev, 2002, 227(1): 93-127.

      [4] EISENBERG R. Trigonal prismatic coordination in tris(dithiolene) complexes: guilty or just non-innocent [J]. Coord Chem Rev, 2011, 255(7/8): 825-836.

      [5] COOMBER A T, BELJONNE D, FRIEND R H, et al. Intermolecular interactions in the molecular ferromagnetic NH4[Ni(mnt)2·H2O] [J]. Nature, 1996, 380(2):144-146.

      [6] DUAN H B, REN X M, MENG Q J. One-dimensional (1D) [Ni(mnt)2]-based spin-peierls-like complexes: structural magnetic and transition properties[J]. Coord Chem Rev, 2010, 254(13/14): 1509-1522.

      [7] URICHI M, YAKUSHI K, YAMASHITA Y, et al. Charge-transfer salts of M(mnt)2(M = Ni, Pd, Pt, Au) with BDNT: ferromagnetic interactions in conductive (BDNT)2-Ni(mnt)2[J]. J Mater Chem, 1998, 8(1): 141146.

      [8] XIE J L, REN X M, SONG Y, et al. Synthesis, crystal structure, and magnetic properties of a novel 1-dimensional nickel(III) chain complex showing ferromagnetic ordering at low temperature [J]. J Chem Soc Dalton Trans, 2002, 14: 2868-2872.

      [9] XIE J L, REN X M, SONG Y, et al. Peculiar magnetic behavior in ion-pair complex [1-(4′-fluorobenzyl)pyridinium][Ni(mnt)2](mnt2-= maleonitriledithiolate) [J]. Chem Commun, 2002, 20: 2346-2347.

      [10] NI C L, DANG D B, SONG Y, et al. An interesting magnetic behavior in molecular solid containing one-dimensional Ni(III) Chain [J]. Chem Phys Lett, 2004, 396(4/6): 353-358.

      [11] NI Z P, REN X M, MA J, et al. Theoretical studies on the magnetic switching controlled by stacking patterns of bis(maleonitriledithiolato) nickelate(III) dimers [J]. J Am Chem Soc, 2005, 127(41): 14330-14388.

      [12] REN X M, MENG Q J, SONG Y, et al. Unusual magnetic property associated with dimerization within a nickel tetramer [J]. Inorg Chem, 2002, 41(23): 5931-5933.

      [13] KISHORE R, DAS S K. Diversities of coordination geometry around the Cu2+center in bis(maleonitriledithiolato)metalate complex anions: geometry controlled by varying the alkyl chain length of imidazolium cations [J]. Cryst Growth Des, 2012, 12(2): 3684-3699.

      [14] NI C L, LI Y Z, MENG Q J. Synthesis, crystal structure and magnetic properties of a new ion-pair complex benzyltriphenylphosphiniumbis(maleonitriledithiolato)nickel [J]. J Coord Chem, 2005, 58(9): 759-766.

      [15] CHEN X, YIN W T, HUANG Q, et al. Syntheses, weak interactions, 3D network structures and magnetic properties of two salts based on bis(maleonitriledithiolate) copper(II) anion and substituted triphenylphosphonium cation [J]. Transition Met Chem, 2010, 35(2): 143-149.

      [16] ZHOU J R, NI C L, YU L L. Syntheses, crystal structures, and magnetic properties of two novel Ni(mnt)2-based molecular magnetic materials containing substituted triphenylphosphonium [J]. Inorg Chim Acta, 2008, 361(1): 400-406.

      [17] CHEN X, LIN J H, ZhOU H L, et al. Two salts containing bis(maleonitriledithiolate)nickel(III)/copper(II) anion and substituted benzyltriphenylphosphinium: syntheses, crystal structures and magnetic properties [J]. Inorg Chim Acta, 2010, 363(14): 4024-4030.

      [18] DAVISON A, HOLM R H, BENSON R E, et al. Metal complexes derived from cis-1,2-dicyano-1,2-ethylenedithiolate and bis(Trifluoromethyl)-1,2-dithiete [J]. Inorg Synth, 1967, 10: 8-26.

      [19] BROOS, R, ANTEUNIS, M. A simplied wittig synthesis of substituted styrenes [J]. Synth Commun, 1976, 6(1): 53-57.

      [20] SHELDRICK G M. SHEXTL-97, programs for crystal structure refinements [CP]. G?ttingen: University of G?ttingen, 1997.

      [21] SHELXTL. Structure determination software programs, version 5.10 [CP]. Madison, Wisconsin: Bruker Analytical X-ray Systems Inc, 1997.

      [22] JOHNSON, M K. Vibrational spectra of dithiolene complexes in dithiolene chemistry [M]. New York: Wiley, 2004: 214-224.

      [23] CHEN X, CHEN W Q, YU L L, et al. Synthesis, structure and magnetic properties of two complexes based on bis(maleonitriledithiolate)nickel(III)/copper(II) anion and 1-(4-Bromobenzyl)triphenylphosphinium [J]. J Mol Struct, 2011, 1006(1/3): 419-424.

      [24] DAI J W, LI B Z, CHEN Y L, et al. Embrace interlocking of dipyrazinylpyridine complexes involving N…π interactions [J]. Inorg Chem Commun, 2010, 13(5): 625-629.

      [25] ZHU H B, CHU Z L, HU D H, et al. Unusual metal-organic frameworks built from 2D layers through Cl...Cl contacts and hydrogen bonds [J]. Inorg Chem Commun, 2007, 10(3): 362-366.

      [26] CHEN W Q, QIAN Y L, CAI H T, et al. Syntheses, crystal structures and magnetic properties of three new molecular solids based on bis(maleonitriledithiolate)copper(II) anion and 2-substituted benzyl triphenylphosphonium [J]. Synth Met, 2014, 196(10): 178-185.

      [責(zé)任編輯:吳文鵬]

      4-sulfonamido-L-prolines as highly efficient organocatalysts for the asymmetric Aldol reaction in water

      LIU Yuxia, Lü Mingxiu, LU Kui, ZHAO Pengfei

      (DepartmentofMaterialandChemistryEngineering,HenanInstituteofEngineering,Zhengzhou450007,Henan,China)

      CLC number: O622 Document code: A

      Article ID: 1008-1011(2016)02-0175-08

      Synthesis, crystal structure and magnetic property of bis (1,2-dithiledithiolene)copperate difluorobenzyl triphenylphosphonium salt

      MAN Limin, WANG Bingwu, ZHENG Wanqi, LIAO Xiaolan, ZHENG Xiaogeng,YANG Zhuohong, NI Chunlin*

      (CollegeofMaterialsandEnergy,InstituteofBiomatrials,SouthChinaAgriculturalUniversity,Guangzhou510642,Guangdong,China)

      Abstract:A new benzyltriphenylphosphonium, [BiFBzTPP]2[Cu(mnt)2] ([BiFBzTPP]+ = 1-(3′,5′-bifluorobenzyltriphenylphosphonium), mnt(2-) = maleonitriledithiolate), was prepared using sodium 1,2-dinitriledithiolate, CuCl2·2H2O, and 3,5-bifluorobenzyltriphenylphosphonium bromide. The title salt crystallizes in the monolinic system, space group P2(1)/n, and the lattice parameters are a = 0.994 9(1) nm, b = 0.154 2(1) nm, c = 0.186 6(1) nm, α = 90°, β = 100.977(3)°, γ = 90°, V = 2.680 1(4) nm3, Z = 2, R1 = 0.049 9, wR(2 )= 0.113 8. The salt consists of two [BiFBzTPP]+ cations and a [Cu(mnt)2](2-) anion. The anions and cations are linked by the C-H…S, C-H…N hydrogen bonds and a p(N)…π stacking interaction. The variable-temperature magnetic susceptibility measurement shows that the title salt exhibited a weak antiferromagnetic coupling behavior when the temperature was decreased. Two diastereomers 4-sulfonamido-L-prolines 1a-b had been efficiently synthesized. The activities and induled stereoselectivities of these organocatalysts were evaluated in the direct asymmetric Aldol reaction of aromatic aldehydes with ketones. By using 5 mol% of the catalysts, the corresponding products of the Aldol reaction were obtained in good yields (up to 93%) with excellent anti diastereoselectivity (up to 94∶6) and enantioselectivity (up to 99% ee) in water.

      Keywords:bis(maleonithiledithiolate)copper(II); substituted benzyltriphenylphosphonium salt; crystal structure; magnetic property diastereomers; organocatalysts; Aldol reaction; aqueous-phase catalysis

      文章編號(hào):1008-1011(2016)02-0169-06

      中圖分類號(hào):O627.51; O614.12

      文獻(xiàn)標(biāo)志碼:A

      作者簡(jiǎn)介:滿麗敏(1991-),女,碩士生,研究方向?yàn)闊o機(jī)功能材料. *通訊聯(lián)系人,E-mail: scauchemnicl@163.com.

      基金項(xiàng)目:廣東省科技計(jì)劃項(xiàng)目( 2014B010105037),華南農(nóng)業(yè)大學(xué)2015年大學(xué)生創(chuàng)新創(chuàng)業(yè)訓(xùn)練計(jì)劃項(xiàng)目(201410564212).

      收稿日期:2015-11-17.

      猜你喜歡
      磁學(xué)芐基苯環(huán)
      福建周寧黃紅壤的磁學(xué)特征及其磁性礦物轉(zhuǎn)化*
      芳香族化合物同分異構(gòu)體的書寫
      立足高考 領(lǐng)悟自招(二)——自主招生怎么考電學(xué)和磁學(xué)
      對(duì)苯環(huán)上一元取代只有一種的同分異構(gòu)體的系統(tǒng)分析
      自主招生真題賞析(二)——考查電學(xué)、磁學(xué)部分
      Z型三叉樹多肽聚苯環(huán)系統(tǒng)的Hosoya指標(biāo)的計(jì)算公式
      脫去含氮芳香雜環(huán)中N-取代芐基的一種新方法
      新型CCR5拮抗劑:N-[1-{5-溴-2-[(4-氯芐基)氧基]芐基}-4-哌啶基]-N-乙基吡啶甲酰胺的合成
      歐盟禁止在化妝品成份中使用3-亞芐基樟腦
      N-(1-(5-溴-2-((4-氯芐基)氧基)芐基)哌啶-4-基)-3-氯-N-乙基苯甲酰胺的合成及表征
      财经| 防城港市| 法库县| 漳浦县| 中阳县| 邯郸市| 岳阳县| 深水埗区| 潜江市| 双辽市| 防城港市| 泰州市| 雷山县| 江阴市| 同仁县| 南丹县| 黑龙江省| 论坛| 宁海县| 井冈山市| 宕昌县| 上虞市| 台南市| 肥东县| 长沙县| 五华县| 广南县| 将乐县| 周宁县| 巴林右旗| 东宁县| 赫章县| 方正县| 东乡| 庄浪县| 壶关县| 太白县| 厦门市| 旌德县| 荔波县| 固原市|