卤化物基质中3m~(2+)离子光谱性质的研究

3m~(2+)离子在红区和红外区可以产生4f~6组态内的f-f跃迁锐线发射和d-f跃迁宽带发射。在某些基质中，这两种跃迁形式可以同时存在。由于d-f跃迁是原于宇称允许的跃迁，所以其发射强度要比4f~n组态内的f-f跃迁强得多。这可以保证对泵浦的有效吸收，提高光泵效率。而4f~n组态内部的f-f跃迁可以实现激光振荡，有利于提高储能降低阈值。所以研究3m~(2+)离子的光谱性质及其影响因素对于寻找和设计新的激光和发光材料有着重要意义。近年来，低价稀大离子的价态问题一直是人们力求探讨的问题，3m~(2+)离子具有极强的还原性和不稳定性，因此关于它的价态研究更具有特殊的意义。本论文采用了几种较简单的方法合成了三十种掺杂3m~(2+)离子的磷光体，分别经x－射线。荧光光谱等实验证实。其中有二十种未见过文献报道。在BaMgF_4:3m~(2+)等十七种体等中研究了基质格位的对称性，对于3m~(2+)离子f－f跃迁性质的影响。如果3m~(2+)离子占据其质中有反演对称中心的点群位置，只有f－f磁偶极跃迁是可能的。这时，~5Do→~7F_1发射线最强。如果3m~(2+)离子占据基质中无反演对称中心的点群位置，f－f磁偶极跃迁和受迫电偶极跃迁都是可能的，这时~5Do→~7Fo发射线最强。在KMgF_3:3m~(2+)等四种体系中研究了电荷补偿效应对3m~(2+)离子f－f跃迁性质的影响。如果3m~(2+)离子取代基质中的一价阳离子，电荷补偿效应使3m~(2+)离子的局部对称性降低，结果f－f跃迁发射线增多。在NaMgF_4:3m~(2+)体系中研究了基质晶体构形变化对3m~(2+)离子f－f跃进性质的影响。NaMgF_3:3m~(2+)由立方相变为正多相时，3m~(2+)离子的点对称性降低，结果出现了~5Do→~7F_3、~5Do→~7F_4两组新线。讨论了晶场强度和化学键性质对于3m~(2+)离子跃迁形式的影响。在有小半径或高正电荷阳离子作为中间阳离子的复合氟化物体系中，3m~(2+)离子周围的晶场变弱，3m－F的共价性降低，结果不能产生d-f跃宽带发射，只能产生f－f跃迁锐线发射。在某些共价性较强的碱金属卤化物和碱S金属卤化物基质中，3m~(2+)离子受到较强的共价作用，这种作用产生主影响，结果能够产生3m~(2+)离子的d-f跃迁宽带发射。在KxNo_1-xMgF_3:3m~(2+)、KMgF_3-xClx:3m~(2+)、KMgF_(2.9)*0.1:3m~(2+) (X=F、Cl、Br、I)三种体系中研究了基质组成变化对3m~(2+)离子f－f跃迁发射强度的影响。在形成化合物或固熔体的条件下，基质组成变化如果导致了3m~(2+)离子对称性降低，3m~(2+)离子的f－f跃迁发射就增强。和阳离子组成的变化相比，阳离子变化对3m~(2+)离子f－f跃迁发射强度影响更大。和正交体等相比，立方体系中基质组成变化对3m~(2+)离子f－f跃迁发射强度的影响更大。在BaCl_2:3m~(2+)等六种体系中讨论了激活剂浓度变化对3m~(2+)离子发射强度的影响。3m~(2+)离子浓度萃取的临界值一般在0.02mol左右，在临界浓度为，随激活剂浓度的增加，3m~(2+)离子的发射强度增大。研究了高温分解3mF_3法制备KMgF_3:3m~(2+)过程中3m(III)→3m(II)的价态转变。由于基质反应的存在，产生了某些局部化学因素，有利于3mF_3的分解，实现了3m(III)→3m(II)的价态转化。在某些复合氟化物和碱S金属氟卤化体系中研究了基质结构因素对于3m~(2+)离子价态的影响。得出了稳定3m~(2+)离子的基质条件为：①基质中含有半径接近3m~(2+)离子的一价或二价阳离子② 复合基质的形成速度要快。找出了KMgF_3、NaMgF_3、BaClF、BaBrF等四种特别能够稳定3m~(2+)离子的基质。在MLnFs(M=Ca Sr Ba Ln=La Crd)考定了几种合成方法对于3m(III)→3m(II)价态转化的影响，其中3m粉还原法为最佳方法。

高Tc超导体R_1Ba_2Cu_3O_(2-x)(R-rare earth)的磁性和超异电性研究

本论文合成了R_1Ba_2Cu_3O_(2-x) (R = La、Nd、Sm、Eu、Gd、Dr、Ho、Er、Tm、Yb)、Y_2Ba_2Cu_3O_(2-x) (x = 0.10～1.17)和Y_1Ba_2Cu_3O_(7-x)S_x (x = 0～2)，并对磁性和超导电性进行了较为系统的研究。R_1Ba_2Cu_3O_(2-x)的磁化率在T > Tc的很宽的温度范围内服从Curic-Weiss定律，求得的有效磁矩略大于理论值，差值与Y_1Ba_2Cu_3O_(2-x)中Cu~(2+)磁矩相近，说明Cu~(2+)的磁矩对体系磁性有额外贡献，这贡献随R~(3+)离子中自旋平行的电子权的增多而增大。其高温下的磁化率CT > 700K)相对Curic-Weiss定律发生较大偏离，这偏离可能的来源有三个：高温下稀土离子发生较大的能级反转效应，高温下结构相变对磁性的影响，高温下氧含量减少造成Cu~(2+)磁矩增大。R_1Ba_2Cu_3O_(2-x)磁化率在T < Tc时也服从Curic-Weiss定律，R~(3+)磁矩是定域的，表明超导与磁性相互独立。互不相关，稀土磁矩与传导电子间无相互作用。用Sr取代R_1Ba_2Cu_3O_(2-x)中的Ba，没能使体系产生磁有序的变化，但却使有效磁矩增大，并完全破坏了样品的超导电性。Sm~(3+)磁化率不服从Curic-Weiss定律，在Sm_1Ba_2Cu_3O_(2-x)中Sm~(3+)显示了典型Van VlccK离子的特性。Y_1Ba_2Cu_3O_(2-x)随氧含量减少发生超导体一半导体一绝缘体的转化，当氧含量由6.90减小至6.49时发生由正交到四方的结构相变。当(7-x) = 5.83时有较多杂质相出现，123相开始分解。样品磁化率均服从Curic-Weiss定律，并随氧含量增大磁化率－温度曲线越来越趋于平缓（直线），当(7-x) = 6.90时磁化率基本不随温度变化，这时Pauli顺磁性占主导地位，这说明氧含量增加定域磁矩减少，求得的有效磁矩Peff随氧含量增大总趋势减小。提出了电子“巡游”的观点，较好地解释了上述现象，并推测出Cu(2)的d电子是离域的，对样品磁矩没有贡献，样品Peff来源于部分Cu(1)的定域Cu~(2+)的磁矩，上述推测被EPR结果证实。正交相Y_1Ba_2Cu_3O_(2-x)的EPR谱显示了中心对称成准立方晶场中Cu~(2+)(d~9, S = 1/2, I = 3/2)的EPR物性。而四方相样品的EPR谱却出现了明显的各向异性，说明观察到的为Cu(1)的EPR信号，由Cu(1)~(2+)的写域磁矩产生。Y_1Ba_2Cu_3O_(2-x)的EPR信号束源于本体相，而非Y_2Cu_2O_5、BaCuO_2、Y_2BaCuO_5等杂质相。各样品EPR信号的自旋浓度远小于1spin/cu，并随氧含量减小而增大，当(7-x) = 6.49、6.40时自旋浓度出现陡增，这时伴随由正交到四方的转化，证明了电子“巡游”观点的正确。用硫部分取代Y_1Ba_2Cu_3O_2g中的氧，当Y_1Ba_2Cu_3O_(2-x)Sx中x = 0.11时Tc = 92.6K，比Y_1Ba_2Cu_3O_(7-x)升高2K，但由于杂质相的存在，ΔTc加宽。其他样品多为半导体和绝缘体。硫取代0，当x = 0.04，0.06，0.11和1.20时磁化率服从Curic-Weiss定律，并且x = 0.87，1.2时分别在230K、240K出现反铁磁有序。其他样品由于Cu被还原为＋1价而变成抗磁性。x = 0.11 (Tc = 92.6K)，EPR谱为正交场中Cu~(2+)的信号。自旋浓度与温度无关。当所有Cu均为Cu~(1+)时，测问的是-s-的EPR信号，而Cu为混合价态(+1和+2时)测问是上述两种信号的叠加。

晶场和化学键性质对Eu~(2+)光谱结构的影响

本工作合成了MF_2:Eu~(2+)(M = Mg、Ca、Sr、Ba); AlF_3:Eu~(2+); Ax:Eu~(2+) (A = Na、k; x = Cl. Br); A_2BeF_4:Eu~(2+) (A = Na、k); ABF_4:Eu~(2+)、A_2SiF_6:Eu~(2+) (A = Na、k、Rb、Cs); NasAl_3F_(14):Eu~(2+)、Na_3AlF_6:Eu~(2+)、K_2MgF_4:Eu~(2+); Al_2O_3:Eu~(2+)、BeAl_2O_4:Eu~(2+)化合物。测定了所含成化合物的晶体结构、荧光光谱、光电子能谱。第一次在AlF_3:Eu~(2+)、 Al_2O_3:Eu~(2+)、BeAl_2O_4:Eu~(2+)中观察到Eu~(2+)的f→f跃迁发射。据我们所知，在单一氧氟化物、单一氧化物中观察到Eu~(2+)的f→f跃迁发射，还是首次。第一次在强晶场、低配位数体系（如：NaBF_4A:Eu~(2+)、Na_2SiFe_6:Eu~(2+)、Na_2BeF_4:Eu~(2+)－K_2BeF_4:Eu~(2+)、Na_5Al_3F_(14):Eu~(2+)）中观察到了Eu~(2+)的f→f跃迁发射。这与Blasse、Fouassier 的观点是不相符的。讨论了Eu~(2+)在所合成化合物中的价态稳定性。Eu~(2+)在所合成化合物中价态是稳定的，从光电子能谱看出尾有少量Eu~(2+)与Eu~(2+)光存。研究了Eu~(2+)的光谱结构与其所处晶场环境、化学键性质的关系。Eu~(2+)的光谱结构由晶场：化学键性质所产生的影响的共同结果来决定。晶场强度是键长的函数，Eu－L化学键的性质除同L有关外，还与邻近的Eu~(2+)的阳离子有关，邻近Eu~(2+)阳离子电负性的大小对Eu－键的共价作用产生很大的影响。采用Sanderson电负性标度计算了 Eu在 MF_2:Eu~(2＋)（M ＝ Mg、Ca、Sr、Br）。AlF_3：Eu~(2+)中所带分电荷，以及Eu－F键的离子性、共价成份。

1. 稀土催化体系异戊二烯本体聚合动力学 2. 不同催化剂对聚异戊二烯甲苯溶液的作用

本文回顾和评述了Ziegler-Natra催化双烯定向聚合的发展，现状及展望，特别是较为详细地讨论了稀土体系的聚合催化剂，聚合机理，聚合动力学以及双烯本体聚合的有关问题。本工作的第一部分内容研究了异戊二烯在Nd(naph)_3 + Al(i-Bu)_3 + Al_2Et_3Cl_3催化体系作用下的本体聚合热效应及本休聚合动力学。指出任本实验条件，温度在-10 ℃ - +5 ℃范围内，聚合体系内温度和聚合环境温度基本一致。在此实验条件下，聚合过程可分为三阶段：聚合初期，聚合活性中心数目尚未稳定，聚合速率逐渐增大，为非稳态聚合阶段；聚合中期，聚合速率恒定，聚合呈稳态特征；聚合后期，聚合为扩散控制阶段。并得到稳太聚合阶段的聚合动力学方程 R_p = k_p[Cat]~(1.96)M. 其聚合反应表观活化能为16.7 kcal/mol。同时考究了聚合物特性粘数和分子量随聚合转化率，聚合催化剂用量，聚合温度等等变化民政部实验结果表明，该催化体系异戊二烯本体聚合仍具有活性聚合的某些特征。本工作的第二部分根据不同催化剂对聚异戊二烯甲苯溶液的作用结果，解释了TiCl_4 + Al(i-Bu)_3催化体系异戊二烯本体聚合转化率很低。聚合产物的凝胶含量较高，而NCl(naph)_3 + Al(i-Bu)_3 + Al_2Et_3Cl_3催化体系异戊二烯本体聚合转化率很容易达到80%。 聚合产物基本不含凝胶的实验事实。实验结果表明，将Ti催化剂加入异戊胶液中，有凝胶生成，且凝胶生成量随催化剂用量的增大而增大。而Nd催化剂不能使异戊胶液生成凝胶。这证实了在异戊二烯本体聚合和溶液聚合中，由于Ti催化剂的阳离子活性，可使线性聚异戊二烯中的不饱合双键发生阳离子反应，生成聚集体结构，星形结构、三维网状结构等三种可能结构的凝胶大分子。从而说明因生成结构紧密的凝胶分子将聚合活性中心紧紧地包围在其中，单体向活性能心扩散困难，致使Ti体系异戊二烯聚合转化率很难提高。根据红外及核磁谱图，Ti或Nd催化剂的加入均未改变聚合物的微观结构，更无环化结构生成。认为聚合物在两催化剂作用下，特性粘数的降低是由于聚合物链存在的不稳定位置及不饱合双键在催化剂的作用下发生了断链或断链后进一步支化所引起的。

青杨(Populus cathayana Rehd)雌雄植株对锈病和干旱胁迫的生理响应及差异蛋白质组比较

雌雄异株植物对环境的不同响应一直是一个有趣而新颖的研究领域，由于雌雄个体不同的繁殖成本及不同的生存策略，使得雌雄植株在生长、存活、生殖格局、空间分布、资源配置等方面已经表现出明显的不同，在生理和分子水平上也表现出明显的性别间差异。干旱是制约农林业发展的环境因子之一，叶锈病是对杨树危害最严重的病害之一，由于长期进化的结果，不同性别的植物必然对生物和非生物胁迫有着不同的响应。本文以雌雄异株的青杨为模式植物，研究雌雄间在生理、生化、亚细胞结构和蛋白质水平上对生物和非生物胁迫的差异响应。主要研究结果如下： （1） 青杨雌雄植株对锈病胁迫的生理生化差异响应 在正常的对照组中，雄株叶片比雌株叶片有着较高的活性氧自由基产生速率、较高的SOD、POD、PPO 和较低的CAT 活性；在锈病感染的早期阶段， SOD、POD、CAT 活性、活性氧自由基产生速率、H2O2 含量、膜脂过氧化程度和细胞膜的电渗率在雌雄株中都增加，而PPO 仅在雄株中增加明显，APX 仅在雌株中增加明显，并且雌株比雄株有着更严重的锈病感染程度、细胞膜的伤害程度和光合系统II 的破坏程度，雌株有更多的净光合速率、气孔导度和叶绿素a 含量的降低，在同工酶变化上，雌雄间对锈病也显示出不同的表达模式。结果显示，雄株比雌株对锈病有着更好的抗性和更有效的ROS 清除系统。 （2） 青杨雌雄植株对干旱胁迫的生理生化及亚细胞结构的差异响应 与较好水分条件相比，干旱下雄株比雌株有着更高的A-Ci 响应参数，如Rubisco 最大羧化速率、光呼吸速率、暗呼吸速率和最大电子传递速率等。干旱显著地增加了膜脂过氧化程度和游离脯氨酸含量，并且雄株比雌株表现出较低的膜脂过氧化程度，较高的总蛋白和游离脯氨酸含量。无论是中度干旱还是极度干旱，除了CAT 外，雄株比雌株表现为较强的抗氧化酶活性，在同工酶谱带上，雌雄间表现出不同的变化模式，并且有些条带是干旱影响应的，而有些条带是性别特异性的，这些性别特异性条带能够作为鉴定性别快速而准确的标记。干旱显著地影响了线粒体、叶绿体和细胞壁的结构，尤其在中度干旱胁迫下，雄株线粒体和叶绿体比雌株呈现出较好的完整性，并且雄株细胞壁要比雌株更厚。因此， 雄株比雌株表现出更强的干旱忍耐性和更高效的抗氧化酶系统。 （3） 青杨雌雄植株对干旱胁迫的蛋白质组差异响应 用双相电泳检测到雌雄间近1000 个蛋白点，通过对比发现对照组雌雄间有54 个差异蛋白点，干旱下雌雄间有108 个差异点，其中102 个被质谱成功鉴定。对照组雌雄间的差异蛋白主要集中在与光合作用相关蛋白、抗氧化酶、胁迫防御蛋白和一些调节基因表达的蛋白；干旱胁迫下雌雄间差异蛋白明显增多，主要有参与信号转导、调节基因表达、蛋白质加工、转录产物的转录翻译后修饰的调节性蛋白蛋白和参与氧化还原平衡、抗胁迫、细胞壁合成、光合作用、能量代谢、氨基酸代谢和脂肪酸代谢等的功能性蛋白。干旱下这些蛋白的表达量在雌雄中有的表现出相同的表达模式，如干旱下雌雄株中Rubisco 激活酶、小热激蛋白等表达都增加，而有的表现出相反的表达模式，如Rubisco 大亚基的降解片段、羰酸酯酶等在雄株中表达量上调而在雌株中却是下调。因此，雌雄间在蛋白质水平上对干旱胁迫响应的差异是显著的，也是复杂的。 It is an interesting and novel topic that dioecious plants possess different responses to environmental stress. As for the different productive cost and different survive strategy, different sexual plants have shown obviously morphological, physiological and molecular differences. Drought is one of the most worldwidely important environmental stress factors that limit plant growth and ecosystem productivity. Rust disease is one of the economically important diseases in many trees. As a result of the long evolutionary process, male and female plants should show different responses to abiotic and biotic stress. In this paper, using a dioeious tree of Populus cathayana Rehd as a model, we study the sexual differences to drought and rust disease stress in physiological, biochemical, sub-cellular and proteomics levels. The main results are follows: (1) The sexual differences in physiology and biochemistry of poplar to rust disease In controls, males showed higher production of superoxide radicals, higher activities of SOD, POD, PPO and lower CAT activity. Under rust disease, the activities of antioxidant, the content of ROS and the degree of cellular member destroyed were increased in both sexes, except for PPO in diseased males and APX in diseased females. However, females showed more seriously disease severity and cellular member and PS II destroyed degrees. Net photosynthesis rate, transpiration rate and chlorophyll a content were decreased more in diseased females than in males. There were also some different changes inantioxidant isozymes under rust disease. The results suggested that male poplar possessed a more effectively antioxidant system and were more resistant to rut disease than females. (2) The sexual differences in physiology and biochemistry of poplar to drought stress Under drought stress, there were higher rates of RuBP-saturated CO2 assimilation, dark respiration, photorespiratory release of oxygen, the max electron transportrate in CO2-saturated and carboxylation efficiency in males than in females. And males showed lower TBARS and higher proline content. Except for CAT, the activities of other antioxidants were higher in males than in females. Meanwhile, there were obviously differences in isozyme changes between teo sexes. Drought stress obviously destroyed the integralities of chloroplasts and mitochondria and the sexual differences in sub-cellular level were obviously under the moderate water stress. Male cell walls were more sensitive to drought stress than did female. The results suggested males were more resistant to drought stress. (3) The sexual differences in proteomics of poplar to drought stress By 2-D and MS analysis, we identified 102 different protein spots between males and females. Under control conditions, the different proteins were mainly in photosynthesis related proteins, antioxidants, stress response proteins and some gene expression related proteins. Under drought stress, the different proteins were focused on (i) regulated proteins such as signaling conduction, kinase, HSP, gene expressional regulation and protein modification, (ii) functional proteins such as photosynthesis, energy metabolism, antioxidant, redox, stress response, lipid metabolism and amino acid metabolism. Some protein showed the same expressional pattern, while some showed contrary expressional pattern. Thus, the results suggested that sexual differences in proteomics were significant and complex.

Chiral ligand 2-(2 '-piperidinyl)pyridine: synthesis, resolution and application in asymmetric diethylzinc addition to aldehydes

Chiral ligand 2-(2'-piperidinyl)pyridine 1 has been synthesized in good overall yield by sequential benzylation, hydrogenation and debenzylation of 2,2'-bipyridine. Its enantiomerically pure enantiomers have been obtained by resolution of 2-(1-benzyl-2-piperidinyl)pyridine 2 with D-tartaric acid (or L-tartaric acid) followed by debenzylation. The absolute configuration was determined by X-ray analysis of the (S)-2 D-tartrate. It was demonstrated that I can be used as an effective enantioselective catalyst in the addition of diethylzinc to aldehydes.

Supramolecular isomerism in zinc hydroxide coordination polymers with pyridine-2,4-dicarboxylic acid: Two polymorphs with centrosymmetric two-dimensional and acentric three-dimensional coordination networks

Reactions of Zn(BF4)(2) and pyridine-2,4-dicarboxylic acid (2,4-pydcH(2)) in the presence of 1,2-bis( 4-pyridyl) ethylene or 1,3-bis(4-pyridyl) propane under hydro(solvo) thermal conditions yielded two polymorphic metal-organic coordination polymers formulated as Zn-2(OH)(2)(2,4-pydc) (1 and 2). Polymorph 1 features a two-dimensional (2-D) layer-like structure that is constructed by 2,4-pydc ligands bridging between the Zn-OH-Zn double-chain units. Each single Zn-OH-Zn chain is composed of mu(2)-OH groups connecting trigonal bipyramidal and tetrahedral Zn centers. Polymorph 2 is a 3-D coordination polymer containing 2-D Zn-OH-Zn sheets that consist of mu(2)- and mu(3)-OH groups and trigonal bipyramidal Zn centers. The sheets are pillared by 2,4-pydc ligands to form an acentric structural architecture. 1 and 2 are rare examples that the two polymorphs exhibit a centrosymmetric 2-D coordination network and an acentric 3-D coordination network, respectively. The different structures lead to differences in photoluminescent properties and thermal stabilities for 1 and 2.

Synthesis, characterization and crystal structure of a new layered heterometallic coordination polymer {[(CuL) Sr-2(H2O)center dot Sr-2(H2O)(7)]center dot 2H(2)O center dot 0.5CH(3)OH}(n)

A copper-strontium heterometallic coordination polymer was synthesized and characterized by elemental analysis and IR spectra. The crystal structure was determined by single-crystal X-ray diffraction analyses. The title complex is a 2 D coordination polymer with the chemical formula [[(CuL)(2)Sr (H2O) center dot Sr-2 ((HO)-O-2)(7)]center dot 2H(2)O center dot 0.5CH(3)OH](n), where H4L = N-(2-hydroxybenzamido)-N'-(3-carboxylsalicylidene) ethylenediamine. Its structural unit is comprised of two adjacent units, which polymerized with each other to form a new layered heterometallic coordination polymer.

Novel two-dimensional sodium molybdenum phosphates containing {M(enMe)(2)}(2+) bridging groups (M = Ni, Cu; enMe=1,2-diaminopropane)

Two novel organic-inorganic hybrid compounds, (H(2)enMe)(4)(H3O)[Ni(enMe)(2)].[Na3Mo12O52P8(OH)(10)].5H(2)O (1) and (H(2)enMe)(4)(H3O)[Cu(enMe)(2)].[Na3Mo12O52P8(OH)(10)].5H(2)O (2) (enMe = 1,2-diaminopropane), have been hydrothermally synthesized and characterized by elemental analyses, IR, EPR, XPS, UV-Vis spectra and TG analyses. Single crystal X-ray diffraction shows that 1 and 2 are isostructural compounds. Both the compounds exhibit an unusual two-dimensional (2-D) window-like network consisting of one-dimensional (1-D) chains of sodium molybdenum phosphate anions connected by transition metal coordination complexes cations. Compound 1 and 2 represent the first 2-D molybdenum phosphate skeleton pillared by transition metal complex fragments.

Synthesis and crystal structure of bis (tert-butyl-cyclopentadienyl)erbium ethoxide, (t-BuCp)(2)ErOEt

The formation of ( t-BuCp)(2)ErOEt was discussed. Its single-crystal structure was determined by X-ray diffraction. The crystal is monoclinic, P2(1)/c space group, a = 1.0191(2), b = 1.6203(5), c = 1.2118(3) nm, beta = 102. 960( 10)degrees, V = 1.9500 (nm(3)), Z = 2, D-c = 1.566 mg . m(-3), R = 0.0450, R-w = 0.1363. The complex is monomeric and solvent-free in the solid state. The erbium ion is coordinated by two tert-butyl-cyclopentadienyl rings and one oxygen atom of ethoxy group to form a seven-coordinated complex.

Hydrothermal synthesis and structure of [Ni(en)(2)V6O14](n)

A new complex [Ni (en)(2)V6O14](n) was hydrothermally synthesized and characterized by 2-dimensional vanadium oxide framework pillared by Ni(en)(2)group. Single crystal X-ray analysis indicates that this compound crystallizes in monoclinic system, space group P2(1)/c with a=0. 892 17(18) nm, b = 1. 711 1(3) nm, c=0. 662 73(13) nm, beta=111. 58(3)degrees, V=0.940 8(3) nm(3), Z=2, D-c=2.501 g/cm(3), R=0. 042 3, omegaR=0. 060 9, S=1. 006.

Novel hydrogen-bonded three-dimensional networks encapsulating one-dimensional covalent chains: [M(4,4 '-bipy)(H2O)4](4-abs)2 center dot nH(2)O (4,4 '-bipy=4,4 '-Bipyridine; 4-abs=4-aminobenzenesulfonate) (M=Co, n=1; M=Mn, n=2)

Two novel compounds, [Co(4,4'-bipy)(H2O)(4)](4-abS)(2).H2O (1) and [Mn(4,4'-bipy)(H2O)(4)](4-abs)(2).2H(2)O (2) (4,4'-bipy = 4,4'-bipyridine; 4-abs = 4-aminobenzenesulfonate), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses, UV-vis and IR spectra, and TG analysis. X-ray structural analysis revealed that 1 and 2 both possess unusual hydrogen-bonded three-dimensional (3-D) networks encapsulating one-dimensional (1-D) covalently bonded infinite [M(4,4'-bipy)(H2O)(4)](2+) (M = Co, Mn) chains. The 4-abs anions in 1 form 1-D zigzag chains through hydrogen bonds. These chains are further extended through crystallization water molecules into 3-D hydrogen-bonded networks with 1-D channels, in which the [Co(4,4'-bipy)(H2O)(4)](2+) linear covalently bonded chains are located. Crystal data for 1: C22H30CoN4O11S2, monoclinic P2(1), a = 11.380(2) Angstrom, b = 8.0274(16) Angstrom, c = 15.670(3) Angstrom, alpha = gamma = 90degrees, beta = 92.82(3)degrees, Z = 2. Compound 2 contains interesting two-dimensional (2-D) honeycomb-like networks formed by 4-abs anions and lattice water molecules via hydrogen bonding, which are extended through other crystallization water molecules into three dimensions with 1-D hexagonal channels. The [Mn(4,4'-bipy)(H2O)(4)](2+) linear covalent chains exist in these channels. Crystal data for 2: C22H32WN4O12S2, monoclinic P2(1)/c, a = 15.0833(14) Angstrom, b = 8.2887(4) Angstrom, c = 23.2228(15) Angstrom, alpha = gamma = 90degrees, beta = 95.186(3)degrees, Z = 4.

Hydrothermal synthesis and structural characterization of a novel P-V-O layered compound [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)8]

A new compound [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)(8)] has been hydrothermally synthesized. Single crystal X-ray analysis indicates that this compound crystallizes in a monoclinic system, space group P2(1)/n with a=1.438 5(3) nm, b=1.012 2(2) nm, c=1.832 5(4) nm, beta=90.21degrees, V=2.668 2 (9) nm(3), Z = 2, D-c = 2.112 g/cm(3), R = 0.055, wR = 0.149 7, S = 1.037. The structure of [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)(8)] is characterized by P-V-O layers constructed by [(VO)4 (OH)(2)(PO4)(4)](6-) non-symmetric units. The P-V-O layers are pillared by [Co(H2O)(2)](2+) group, resulting in the channels within which the protonated diaminoethane and H3O+ are located.

Interactions of thiamine monophosphate (TMP) with one- and two-dimensional polymeric halogenomercurate anions. Crystal structures of (TMP)(Hg2Br5)center dot 0.5H(2)O and (TMP)(2)(Hg3I8)

An investigation into the interactions between thiamine monophosphate (TMP) and anions has resulted in the preparation and X-ray characterization of the compounds (TMP)(Hg2Br5).0.5H(2)O (1) and (TMP)(2)(Hg3I8) (2). In each compound the TMP molecule exists as a monovalent cation in the usual F conformation. The halogenomercurate anions occur in two-dimensional (2-D) network in 1 or one-dimensional (1-D) chain in 2. In both 1 and 2, the structures consist of alternating cationic sheets of the hydrogen-bonded TMP molecules and anionic sheets of the polymeric halogenomercurate anions. The TMP molecule binds to the polymeric anions through the characteristic 'anion bridge I', C(2)-H..X...pyrimidinium (X = Br in 1 and 1 in 2), and electrostatic interactions between electropositive S(1) and halogen atoms. The 'anion bridge II' of the type N(4'1)-H...X...thiazolium (X = phosphate group) plays a role in stabilizing the molecular conformation. The biological implication of the host-guest-like complexation between TMP and polymeric anions is discussed.