碳氟醇对阳离子表面活性及胶团反离子结合度的影响

用表面张力及电动势法研究了Ｃ１０Ｈ２１Ｎ（ＣＨ３）３Ｂｒ，Ｃ１２Ｈ２５Ｎ（ＣＨ３）３Ｂｒ和Ｃ３Ｆ７ＣＨ２ＯＨ混合水溶液的表面与胶团性质。结果表明，对于阳离子表面活性剂，Ｃ３Ｆ７ＣＨ２ＯＨ的加入一方面增加表面活性，另一方面降低胶团反离子结合度。后者不同于阴离子表面活性剂／Ｃ３Ｆ７ＣＨ２ＯＨ混合体系，可归因于Ｃ３Ｆ７ＣＨ２ＯＨ略有酸性，因而具备一些类似阴离子表面活性剂的性质。     

双（取代环戊二烯基）二氯化钛的晶体结构分析

报道了双（１－正戊基环己基茂）二氯化钛［（η５－Ｃ５Ｈ４Ｃ（ＣＨ２）５（Ｃ５Ｈ１１－ｎ］２ＴｉＣｌ２（Ｉ）及双（１－甲基－１－（α－噻吩基）乙基环戊二烯基）二氯化钛［η￣５－Ｃ５Ｈ４Ｃ（ＣＨ３）＿２－］２ＴｉＣｌ２（Ⅱ）的晶体结构和分子结构。二者均系单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，晶胞参数ａ＝１４．１８０（２），ｂ＝６．５６２（１），ｃ＝１７．０４６（３），β＝９９．６３（１）°，Ｚ＝２，Ｖ＝１５６３．８，Ｄｘ＝１．１８８ｇ／ｃｍ３，Ｆ（０００）＝５９６，Ｍｒ＝５５３．５６，λ＝０．７１０７３μ＝４．５９ｃｍ－１，Ｒ＝０．０５８，Ｒｗ＝０．０６６；（１）的空间群为Ｃ２／ｃ，晶胞参数ａ＝２５．７１３（１），ｂ＝６．６１７（１），ｃ＝１３．５９１（１），β＝９２．７８（２）°，Ｚ＝４，Ｖ＝２３０９．８，Ｄｘ＝１．４３０ｇ／ｃｍ３，Ｍｒ＝４９７．４１，λ＝０．７１０７３，μ＝７．８２２ｃｍ－１，Ｆ（０００）＝１０３２，Ｒ＝０．０５５，Ｒｗ＝０．０７２。茂环上取代基对茂环金属化合物的结构产生较大影响，空间阻碍的增大使得取代基与茂环相连Ｃ－Ｃ单键增长。     

三环己基锡O，O＇－二（4－氯苯基）二硫代磷酸酯和二丁基锡双［O，O＇－二（4－甲基苯基）二硫代磷酸酯］的分子和晶体结构

三环己基锡Ｏ，Ｏ＇－二（４－氯苯基）二硫代磷酸酯（Ⅰ），Ｃ＿（３０）Ｈ＿（４１）Ｃｌ＿２Ｏ＿２ＰＳ＿２Ｓｎ，Ｍ＿ｒ＝７１８．３６，单斜晶系，Ｐ２＿１／ｎ，ａ＝１６．１５１（２），ｂ＝９．４１５（１），ｃ＝２２．９８７（３），β＝１０５．６９（１）°，Ｚ＝４，Ｄｃ＝１．４１８ｇ·ｃｍ￣（－３），Ｒ＝０．０６３；二丁基锡双［Ｏ，Ｏ＇－二（４－甲基苯基）二硫代磷酸酯］（Ⅱ），Ｃ＿（３６）Ｈ＿（４６）Ｏ＿４Ｐ＿２Ｓ＿４Ｓｎ，Ｍ＿ｒ＝８５１．６６，单斜晶系，Ｐ２＿１／ｃ，ａ＝１２．２８４（４），ｂ＝９．８０７（１），ｃ＝３４．４７１（８），β＝９９．０２（２）°，Ｚ＝４，Ｄ＿ｃ＝１．３７９ｇ·ｃｍ（－３），Ｒ＝０．０４２。化合物Ⅰ具有单分子的四配位变形四面体结构。其Ｓｎ－Ｓ（１）键长为２．５０１（２）；而Ｓｎ与Ｓ（２）的原子间距则为３．５９７；化合物Ⅱ具有单分子的六配位变形八面体结构，其Ｓｎ－Ｓ（１），Ｓｎ－Ｓ（２），Ｓｎ－Ｓ（３）和Ｓｎ－Ｓ（４）的键长分别为２．４９５（３），２．４９３（２），３．２４４（４）和３．２２８（３）。     

三环己基锡O,O‘—二（4—氯苯基）—二硫代磷酯酯和二丁基锡双（O,O’—二…

三环己基锡Ｏ，Ｏ’－二（４－氯苯基）二硫代磷酸酯（Ｉ），Ｃ３０Ｈ４１Ｃｌ２（Ｏ２ＰＳ２Ｓｎ，Ｍｒ＝７１８．３６，单斜晶系，Ｐ２１／ｎ，ａ＝１６．１５１（２），ｂ＝９．４１５９（１），ｃ＝２２．９８７（３），Ａ，β＝１０５．６９（１）°，Ｚ＝４，Ｄｃ＝１．４１８ｇ．ｃｍ＾－３，Ｒ＝０．０６３；二丁基锡双（Ｏ，Ｏ’－二（４－甲基苯基）二硫代磷酯酯（Ⅱ），Ｃ３６Ｈ４６Ｏ４Ｐ２Ｓ４Ｓｎ，Ｍｒ＝８５１．６６     

双（取代环戊二烯基）二氯化锆的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了双［１－苄基－１－乙基丙基环戊二烯基］二氯化锆［η５－Ｃ５Ｈ４Ｃ（Ｃ２Ｈ５）２ＣＨ２Ｃ６Ｈ５］２ＺｒＣｌ２（Ｉ）及（１，２－二异丁基－１，２－甲基－乙基桥联）双环戊二烯基二氯化锆［η５－Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ５Ｈ４－η５］ＺｒＣｌ２（Ⅱ）的结构。二者皆为单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，ａ＝１２．５８２（３），ｂ＝７．９９２（２），ｃ＝１４．９７９（３）Ａ，β＝１０１．６８（１）°，Ｖ＝１４７４．９（９）Ａ３，Ｍｒ＝６１２．８４，Ｚ＝２，Ｄｘ＝１．３８ｇ／ｃｍ３，μ＝５．６９ｃｍ（－１），Ｆ（０００）＝６４０，Ｒ＝０．０３３，Ｒω＝０．０３６。（Ⅱ）的空间群为Ｃｃ，ａ＝１３．３０９（３），ｂ＝９．５９１（１），ｃ＝１６．４４９（８）Ａ。β＝４．８３（３）°，Ｖ＝２０９．２（２）Ａ３，Ｍｒ＝４５８．６３，Ｚ＝４，Ｄｘ＝１．４５６ｇ／ｃｍ３，μ＝７．７７ｃｍ（－１），Ｆ（０００）＝９５２，Ｒ＝０．０５１，Ｒω＝０．０６１。化合物（Ｉ）以重叠式存在，两个苄基处于反式。晶体（Ⅱ）以交叉式存在，甲基、异丁基以反式构象存在。     

琥珀酸二(2-乙基己基)酯磺酸钠与聚合物表面活性剂形成的混合反胶团研究

研究了琥珀酸二（２－乙基已基）酯磺酸钠（ＡＯＴ）与聚合物表面活性剂混合后在非极性溶剂中的聚集行为。结果表明,随聚合物与ＡＯＴ摩尔比的增大,体系的ＣＭＣ逐渐增大,但该摩尔比大于１：１时,用水增溶法不能测出ＣＭＣ;研究了荧光探针Ｒｕ（ｂｐｙ＾３＾２＋在该混合反胶团中的荧光行为,随有机相含水量Ｗ０增大,对微极性敏感的荧光探针的最大发射波长λｍａｘ逐渐红移,荧光强度Ｆ则逐渐减弱。随聚合物含量增大,混合体系     

［Mn_2（bzacen）_2（MeOH）_2（μ－4，4′－bipy）］（ClO_4）_2的合成、结构和谱学性质

合成了［Ｍｎ_２（ｂｚａｃｅｎ）_２（ＭｅＯＨ）_２（μ－４，４′－ｂｉｐｙ）］（ＣｌＯ_４）_２化合物，并测定其晶体结构。该晶体属单斜晶系，空间群Ｐ２_１／ｎ，晶胞参数：ａ＝１．３０８２（３）ｎｍ，ｂ＝１．２７１３（３）ｎｍ，ｃ＝１．８００６（５）ｎｍ，β＝１１０．９１（２）°，Ｚ＝２，μ＝５．９７ｃｍ－１，Ｒ＝０．０５８０，ＧＯＦ＝１．６６．在配合物阳离子中，４，４′－联吡啶桥联２个［Ｍｎ（ｂｚａｃｅｎ）（ＭｅＯＨ）］＋，而锰原子具有３个Ｎ原子和３个Ｏ原子形成的扭曲八面体配位构型。红外光谱和拉曼光谱均表明，形成配合物后，ｖ_（Ｃ＝Ｎ）、ｖ（Ｃ＝Ｏ）、和ｖ（Ｃ＝Ｃ）移向低频。红外光谱的１１１０ｃｍ￣（－１）谱带表明ＣｌＯ_４￣－未与Ｍｎ（Ⅲ）配位，８１２ｃｍ￣（－１）振动说明４，４′－ｂｉｐｙ充当桥联二齿配体。拉曼光谱中的４６３ｃｍ￣（－１）和４０１ｃｍ￣（－１）别为Ｍｎ－Ｏ和Ｍｎ－Ｎ的振动带。电子光谱证明存在ｄ－ｄ、ｄ－π和π－π跃迁。电极电位测定显示该配合物Ｍｎ（Ⅲ）的价态是稳定的。     

Mn（Ⅲ）—苯甲酰丙酮缩乙二胺—有机碱配合物的合成及结构

合成了４种锰（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物：Ｍｎ（ｂｚａｃｅｎ）ＬＣｌＯ４．（Ｌ为哌嗪，吡啶，γ－甲基吡啶和乙腈）。测定了配合物［Ｍｎ（ｂｚａｃｅｎ）（ＣＨ３ＣＮ）ＣｌＯ４］的结构，晶体属正交晶系。空间群Ｐｎｍａ。晶胞参数：ａ＝０．９０７７（１），ｂ＝１．５５６３（１）ｎｍ，ｃ＝１．７２０５（２）ｎｍ，Ｖ＝２．４３０５ｎｍ＾３，Ｚ＝４，Ｄｃ＝１．４８ｇ／ｃｍ＾３，Ｄｍ＝１．４９ｇ／ｃｍ＾     

四甲基双硅桥联环戊二烯基稀土金属有机配合物的合成及［Me_4Si_2（C_5H_

四甲基双硅桥联环戊二烯基钠与无水三氯化稀土在ＴＨＦ溶剂中反应合成了标题配合物Ｍｅ１Ｓｉ２（Ｃ５Ｈ４）２ＬｎＣｌ［Ｌｎ：３Ｎｄ，４Ｓｍ，５Ｇｄ，６Ｙ］和配合物Ｍｅ４Ｓｉ２（Ｃ５Ｈ４）：Ｌｎ（Ｃ５Ｈ５）（ＴＨＦ）ｎ［Ｌｎ：１Ｌａ，ｎ＝１；２Ｐｒ，ｎ＝０］。通过元素分析、１ＨＮＭＲ、１３ＣＮＭＲ和ＭＳ确证了配合物的结构，在ＴＨＦ溶液中重结晶获得配合物４的单晶，ｘ射线衍射证明晶体结构为二聚体，４为单斜晶系，空间群为Ｐ２１／ｃ，晶体学数据ａ＝１．２９８２（３）ｎｍ，ｂ＝１．２２６９（３）ｎｍ，ｃ＝１．３６８１（２）ｎｍ，β＝９６．７９（２）°，Ｖ＝２．１６２（１）ｎｍ３，Ｚ＝２，Ｄｘ＝１．５３ｇ／ｃｍ３，偏差因子Ｒ＝０．０６８。     

1-(4-磺酸基苯基)-3-[4-(苯基偶氮)苯基]-三氮烯与季铵盐型阳离子表面活性剂的显色反应及应用

合成了１－（４－磺酸基苯基）－３－［４－（苯基偶氮）苯基］－三氮烯（ＳＰＡＰＴ）,研究了该试剂在强碱性介质中与季铵盐型阳离子表面活性剂溴化十六烷基吡啶（ＣＰＢ）和溴化十六烷基三甲铵（ＣＴＭＡＢ）的显色反应体系,试剂与表面活性剂形成１∶３的紫红色离子缔合物,其表观摩尔吸光系数分别为１．６７×１０４和１．０６×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。测定了显色体系中ＣＰＢ和ＣＴＭＡＢ的临界胶束浓度（ＣＭＣ）,证明在比尔定律范围内,ＣＰＢ和ＣＴＭＡＢ均以单分子缔合显色。确定了显色体系最佳实验条件     

正、负离子表面活性剂混合水溶液的相行为

通过对混合系统相行为的研究，总结出正、负离子表面性剂混合体系普遍存在三上浓度区的规律，即在低浓度与高浓度时为透明均相溶液，中间浓度区为复相体系，而且表明，随极性基体积增大，混合体系形成均相溶液的能力增加；在高浓度区，疏水链长短对混合体系形成均相溶液能力的影响与低浓度区的情况不完全一致，有时会出现疏水链较短的体系形成均相溶液的能力反而较差的“反常”现象。     

C12-2-En-C12•2Br与SDS混合水溶液的胶团化研究

与[C12H25N＋(CH3)2CH2]2•2Br－(简记为C12-2-C12•2Br)/ C12H25SO4Na(SDS)混合水溶液相比,随着联接链上乙氧基团(E)数目增加,[C12H25N＋(CH3)2]2C2H4(OC2H4)n•2Br－(简记为C12-2-En-C12•2Br, n=2,3)与SDS混合水溶液澄清区域明显增大. C12-2-E3-C12•2Br/SDS混合胶团化过程中二组分产生了协同效应,理论预测在澄清区域所能达到的最小临界胶团总浓度(cmcT,min)= 0.0339 mmol•L－1,对应的SDS在溶液体相中的摩尔分数(x2*)=0.447.当水溶液体相中SDS摩尔分数(x2)=0.5时,混合胶团总聚集数(NT)=36,混合胶团中SDS的摩尔分数(x2M)=0.43.     

全氟壬烯氧基苯磺酸钠与烷基季铵盐的相互作用

通过六氟丙烯三聚体(全氟壬烯)氧基苯磺酸钠(C₉F₁₇OC₆H₄SO₃Na, OBS)与阳离子碳氢表面活性剂C_nNR[C_nH_2n+1N(CH₃)₃Br, C_nNM, n=8, 10和C_nH_2n+1N(CH₂CH₃)₃Br, C_nNE, n=8, 10, 12]复配, 研究了OBS与C_nNR的摩尔比、 C_nNR疏水链长及C_nNR亲水基团大小对此类阴、 阳离子碳氟-碳氢表面活性剂混合体系的临界胶束浓度(cmc)、 最低表面张力(γ_cmc)、 总饱和吸附量(Γ_tm)及极限分子面积(A_min)的影响. 结果表明, 通过与C_nNR复配, OBS的cmc和γ_cmc均大幅下降, 达到了全面增效的结果. 不同摩尔比的OBS-C₈NE混合体系中, 摩尔比为1:1时表面活性最好, cmc和γ_cmc均最小; 偏离等摩尔比时, OBS过量时混合体系的cmc小于C₈NE过量时混合体系的cmc, 但γ_cmc相差不大. 与单体系相比, OBS-C₈NE混合体系的Γ_tm明显增大、 A_min明显变小. OBS与不同疏水链长的C_nNE复配时, cmc的变化规律为C₈NE>C₁₀NE>C₁₂NE, 表明C_nNE疏水链长的增加能降低混合体系的cmc. 通过比较C_nNM和C_nNE(n=8, 10)的表面活性发现, 改变混合体系中C_nNR的亲水基团大小对混合体系的表面活性无明显影响.     

阳离子碳氢/碳氟表面活性剂与中性高聚物相互作用的研究

研究了阳离子碳氢表面活性剂十二烷基三烷基溴化铵[C12H25N(CnH2n＋1)3Br, n＝1, 2, 3, 4]和阳离子碳氟表面活性剂F[CF(CF3)CF2O]2CF(CF3)CONH(CH2)3N(C2H5)2CH3I (FCI-2)分别与中性高聚物聚氧乙烯(PEO, 分子量20000)和聚氧乙烯-聚氧丙烯三嵌段共聚物[(EO)76(PO)29(EO)76, F68]的相互作用. 结果表明, 所用的碳氢阳离子表面活性剂与PEO和F68均无相互作用, 但碳氟阳离子表面活性剂FCI-2与PEO和F68均具有明显的相互作用, 而且F68与FCI-2的相互作用强于PEO与FCI-2体系. 结果也初步表明碳氟表面活性剂与高聚物的相互作用强于碳氢表面活性剂-高聚物体系.     

Liquid crystals of silver complexes derived from simple 1-alkylimidazoles

A homologous series of silver complexes of 1-alkylimidazoles (R-im, R = CnH(2n+1), where n= 10, 12, 14, 16 and 18) was synthesized. All the CnH(2n+1)-im ligands are non-mesomorphic. Upon complexation, all the [Ag(CnH(2n+1)-im)2]-[NO3], except for n = 10, exhibit liquid crystalline properties. The crystal structure of [Ag(C12H25-im)2][NO3] shows that the silver center is two-coordinate and adopts a U-shaped conformation with bilayer packing. The non-mesomorphic [Ag(C16H33-bim)2][NO3](bim = benzimidazole) has a three-coordinate silver ion and has a chair conformation with monolayer stacking. Non-mesomorphic [Ag(C16H33-bim)2][BF4] has a linear geometry around the silver ion and also has a chair conformation. The mesophase for the Ag-(CnH(2n+1)-im) complexes has been identified as the smectic A (SmA) phase. [Ag(C16H33-im)2]+ with four different anions, NO3-, BF4-, PF6- and CF3SO3- were compared. Of the four Ag-im complexes, only that with the CF3SO3- anion does not show liquid-crystal behavior.     

Aggregation behavior of a series of anionic sulfonate gemini surfactants and their corresponding monomeric surfactant

A series of anionic sulfonate gemini surfactants with the general structure of [(Cn H2n+1)(C3H6SO(-)3) NCsN(C3H6SO(-)3)(CnH2n+1)].2Na+ have been synthesized. While the spacer group Cs represents p-xylyl or (CH2)3, the surfactants are abbreviated as CnCpxCn(SO3)2 (n=8,10,12) or C12C3C12(SO3)2(n=12), respectively. A corresponding monomeric surfactant C12H25N(CH3)(C3H6SO(-)3).Na+(C12NSO3) has also been prepared. The aggregation behavior of these surfactants has been studied at pH 9.2 and ionic strength of 30 mM. The gemini surfactants exhibit stronger aggregation tendencies and much less endothermic enthalpy changes of micellization (DeltaH mic) compared with the monomeric surfactant. The critical micelle concentrations (CMC) of the gemini surfactants decrease with the increase of the hydrophobic chain length from C8CpxC8(SO3)2 to C10CpxC10(SO3)2, but the CMC values of C10CpxC10(SO3)2 and C12CpxC12(SO3)2 are very close. The DeltaH mic values vary from endothermic for C8CpxC8(SO3)2 to almost zero for C12CpxC12(SO3)2. Besides, vesicles are observed above the CMC for all these surfactants. The water-mediated intermolecular hydrogen bonding between the tertiary nitrogen groups may assist C12NSO3 and C12C3C12(SO3)2 in their vesicle formation, while the pi-pi interaction between aromatic rings should be another additional driving force for the vesicle formation of CnCpxCn(SO3)2. Meanwhile, the hydrogen bonding, pi-pi interaction, and strong hydrophobic interaction provide the possibility of a multilayer formation for C12CpxC12(SO3)2 and C12C3C12(SO3)2 at the air/water interface, which is a possible reason for the extremely small minimum area occupied per surfactant molecule at the air/water interface for these two gemini surfactants.     

二(1-正丁基茚基)四羰基二钌的合成与晶体结构

由C9H6-n-BuH与Ru3(CO)12在二甲苯中加热回流, 合成了一个新的双核配合物(η5-C9H6-n-Bu)2Ru2(CO)4. 通过元素分析、红外光谱、核磁共振氢谱对其结构进行了表征. 用X射线单晶衍射法测定了(η5-C9H6-n-Bu)2Ru2(CO)4的结构, 结果表明: 晶体属于三斜晶系, Pī空间群, a＝0.8880(5) nm, b＝1.2337(8) nm, c＝1.3235(8) nm, α＝83.054(12)°, β＝76.683(10)°, γ＝77.036(12)°, V＝1.3713(15) nm3, Dc＝1.588 g•cm－3, m＝1.134 mm－1, F(000)＝658, Z＝2, R1＝0.0993, wR2＝0.2459.     

Hydrophilicity of Polar and Apolar Domains of Amphiphiles

The hydrophilicity of polar and apolar domains of various amphiphiles was systematically estimated for their homologues and analogues by measuring the molar adiabatic compressibility of an aqueous solution at infinite dilution. The homologues of protic alkyl H(CH(2))(n)-, perfluoroalkyl F(CF(2))(n)-, and alkylphenyl H(CH(2))(n)(C(6)H(5))- groups (n=0-10) were chosen to represent apolar hydrophobic domains. The polar hydrophilic domains tested were -SO(4)Na, -SO(3)Na, -COONH(4), -N(CH(3))(3)Br, N(C(m)H(2m+1))(4)Br (m=1-5), and -NH(CH(2))(n)SO(3) (n=3, 4) groups. Also tested were the tetraphenyl ionic compounds (C(6)H(5))(4)MX (M=B/X=Na, M=P/X=Cl, M=As/X=Cl) to study the effect of the ionic sign of the core atom across the tetraphenyl apolar shell, the polyethylene glycols H(OCH(2)CH(2))(m)OH (m=1-4) to study the role of apolar -CH(2)- units in the hydrophilic oxyethylene group, and the zwitterionic dimethylaminoalkylsulfonate (CH(3))(2)NH(CH(2))(n)SO(3) homologues to study the effect of intramolecular salt formation on the hydrophilicity of the zwitterion. The adiabatic compressibility of the solution was calculated from measurement of the sound velocity and density of solutions. The introduction of laboratory automation and the numerical control of the system improved the accuracies and efficiencies of the measurements a great deal. The range of the temperature scan was 0-40 degrees C with an effective accuracy of +/-0.001 degrees C and the concentration was automatically scanned down to far below the cmc of the surfactant. The hydrophilicity of various polar and apolar substances was estimated as the decrease of molar adiabatic compressibility of the aqueous solution with increased concentration of their homologues and analogues. The hydrophobic hydration of nonpolar substances was found to be very small at room temperature and was barely detected above 40 degrees C; however, it became large as the temperature was lowered and attained a maximum at 0 degrees C. The cationic charge of quaternary ammonium N(+)(C(n)H(2n+1))(4) was found to enhance the hydrophobic hydration of methylene groups located at a distance of 4 to 6 ? from the core nitrogen atom, while the terminal negative charge of the anionic surfactant R-SO(4)(-), R-SO(3)(-), or R-COO(-) was found to decrease the hydrophobic hydration of -CH(2)- units within the same range. The hydrophilicity of quaternary ammonium and the tetraphenyl ions should be synergistically given by both hydrophobic and ionic hydrations. The hydrophilicity of the perfluoromethylene unit -CF(2)- was found to have a value comparable to that of the protic methylene unit -CH(2)-. The hydrophobic hydration seems to offer a good measure of the hydrophilicity of apolar substances; however, it does not necessarily represent the "hydrophobicity" of the apolar segment when the "surface activity" of the amphiphile is concerned. Copyright 2000 Academic Press.     

普鲁士蓝类配位聚合物KCd[Cr(CN)6]•H2O的合成、 结构及多孔性能研究

以Cd2＋和[Cr(CN)6]3－为建筑基元通过自组装合成普鲁士蓝类配位聚合物KCd[Cr(CN)6]•H2O (1•H2O), 并用红外光谱、元素分析、单晶X射线衍射、粉末X射线衍射、热重分析和氮气吸附脱附等手段对其进行了表征. 配位聚合物1•H2O属于面心立方晶系, 空间群Fm-3m, 晶胞参数: a＝b＝c＝1.09059 mn, α＝β＝γ＝90°. 配位聚合物1•H2O是由K＋, Cd2＋, [Cr(CN)6]3－离子和一个结晶水分子组成的三维多孔结构. 热重分析结果表明失水样品1的骨架结构在120～ 200 ℃之间保持稳定. 氮气吸附脱附研究表明: 失水样品1具有683.6 m2•g－1的比表面积, 氮气最大吸附量为8.83 mmol•g－1.     

3-羟基克拉霉素和2′-乙酰基-3-氧代克拉霉素的合成与晶体结构

克拉霉素在不同条件下水解, 分别生成3-羟基克拉霉素(2)和3-羟基-8,9,10,11-二脱水-9,12-半缩酮克拉霉素(3), 用乙酸酐保护2的C(2’)-OH得到2′-乙酰基-3-羟基克拉霉素(4), 用N-氯代琥珀酰亚胺(NCS)氧化4的C(3)—OH合成了2’-乙酰基-3-氧代克拉霉素(5), 采用MS, IR, 1H NMR, 13C NMR等对这些化合物进行了表征. 用X射线单晶衍射法测定了化合物2和5的晶体结构, 其均属于正交晶系, P212121 空间群. 化合物2的晶胞参数a＝1.3657(3) nm, b＝1.4783(3) nm, c＝1.6510(3) nm, Z＝4, V＝3.3332(12) nm3, Dc＝1.175 g/cm3, F(000)＝1288, μ＝0.087 mm－1; 化合物5的晶胞参数 a＝1.5124(3) nm, b＝1.5247(3) nm, c＝1.5288(3) nm, Z＝4, V＝3.5254(12) nm3, Dc＝1.187 g/cm3, F(000)＝1368.0, μ＝0.088 mm－1.