Structural Manipulation and Properties of Silver-based Coordination Complexes

银离子可以呈现四种氧化态，零价，一价，二价和三价，其中一价银化合物最为常见。一价银离子的电子构型为[Kr]4d105s0，属于闭壳层的电子构型，其配位数可以从二配位到八配位变化。另外，几何上临近的一价银离子由于5s和5p轨道能级与4d轨道能级接近，因此它们彼此倾向形成银银弱的作用，被称为“亲银作用”。正是由于银离子与众不同的特点，使得含银功能配位聚合物及簇合物的组装，调控及光电性质研究已经成为当今化学研究中最活跃的研究热点之一。 本论文的主要内容如下： 一、两个系列的含银配位聚合物的组装和调控。(1)利用不同的阴离子，合成了三个银/氨基吡嗪配位聚合物(1-3)，另外通过引入多功能的羧酸配体...It is known that silver can appear in three states of oxidation, +1, +2 and +3. Among them, Ag(I) complexes are well-known. Ag(I) possesses closed-shell electronic configuration ([Kr]4d105s0) and shows versatile coordination numbers ranging from 2 to 8. Moreover, adjacent Ag(I) ions are inclined to form Ag-Ag interaction, called ‘argentophilicity’. Due to above-mentioned characteristics of Ag(I), ...学位：理学博士院系专业：化学化工学院化学系_无机化学学号：2052008015015

5-Bromo-2,3-dihydro-1H-cyclo­penta­[a]naphthalen-1-one

The title compound, C13H9BrO, has been synthesized by the intra­molecular Friedel–Crafts reaction of 1-(1-bromo-4-naphth­yl)-3-chloro­propan-1-one. There are two approximately planar [maximum deviations of 0.8 (2) and 0.4 (2) Å in the two mol­ecules] molecules in the asymmetric unit. The dihedral angle between their mean planes is 19.72 (8)°. Weak inter­molecular C—H⋯O hydrogen bonding is present in the crystal structure

介孔氧化铝负载Ni-Co氧化物催化剂上丙烷氧化脱氢制丙烯(英文)

以非离子型三嵌段共聚物作为模板剂,异丙醇铝为氧化铝的前驱物,采用一锅法合成了一系列介孔氧化铝负载镍氧化物、钴氧化物以及镍-钴双金属氧化物催化剂,并以介孔氧化铝为载体,采用浸渍法制备了负载Ni-Co氧化物催化剂.采用N2吸附-脱附、高分辨透射电镜(HRTEM)、X射线粉末衍射(XRD)、H2程序升温还原(H2-TPR)以及激光拉曼光谱(LRS)等技术对催化剂的结构与性质进行表征,并考察了催化剂的丙烷氧化脱氢反应性能.结果表明:一锅法制备的各催化剂均有大的比表面积和规整的孔道结构,且负载的金属氧化物高度分散;而浸渍法制备的催化剂,其载体的介孔结构被破坏并有Co3O4晶相生成.在考察的催化剂中,一锅法合成的介孔氧化铝负载Ni-Co氧化物催化剂表现出最佳的丙烷氧化脱氢性能.在450℃、C3H8:O2:N2的摩尔比为1:1:4和空速(GHSV)为10000mL·g-1·h-1条件下,该催化剂上丙烯产率为10.3%,远高于浸渍法制备的催化剂上所获得的丙烯产率(2.4%).关联催化剂表征和反应结果,讨论了催化剂结构与性能之间的关系

4H-Cyclo­penta­[def]phenanthren-4-one

In the title compound, C15H8O, the asymmetric unit contains four independent mol­ecules and crystallizes with aromatic π–π stacking inter­actions[centroid–centroid distances = 3.5326 (18) Å]

Series of Ag(I) Coordination Complexes Derived from Aminopyrimidyl Ligands and Dicarboxylates: Syntheses, Crystal Structures, and Properties

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] series of new metal organic frameworks, namely, [Ag(mapym)(suc)(0.5)center dot 0.5H(2)O](n) (1), [Ag-2(mapym)2(glu)center dot 1.5H(2)O] (2), [Ag-2(mapym)(2)(ipa)center dot 2H(2)O](n) (3), [Ag-2(mapym)(2)(tpa)(H2O)](n) (4), [Ag(dmapym)(2)(ox)(0.5)center dot H2O] (5), and [Ag(dmapym)(bbdc)(0.5)center dot 0.5H(2)O](n) (6) (mapym = 2-amino-4-methylpyrimidine, dmapym = 2-amino-4,6-dimethylpyrimidine, H(2)suc = succinic acid, H(2)glu = glutaric acid, H(2)ipa = isophthalic acid, H(2)tpa = terephthalic acid, H(2)ox = oxalic acid, H(2)bbdc = 4,4-bibenzenedicarboxylic acid), have been synthesized and structurally characterized. Complexes 1 and 2 exhibit two-dimensional (2D) interpenetrated and double-sheet structures, respectively. Complex 3 is a three-dimensional (3D) framework constructed through unusual 2D -> 3D parallel interpenetration of a corrugated 2D 4(4)-sql net. Complex 5 is a 0-dimensional (0D) H-shaped molecule, and the self-complementary N-H center dot center dot center dot N hydrogen bonds incorporating R-4(4)(14) hydrogen bond motifs extend these molecules into a 3D supramolecular framework. Complexes 4 and 6 are also 2D sheets constructed with a similar fashion to that of 1 and 2 but with aryl-dicarboxylate as bridge. The results show that the coordination geometry of the Ag(I) ions and the configuration and coordination mode of dicarboxylates as well as the competition between steric and electronic effects of methyl groups on aminopyrimidyl ligands play crucial roles in determining the structure of the complexes. Additionally, results about IR spectra, thermogravimetric curves, and photoluminescence spectra were addressed.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Low dimensional metal-organic frameworks (MOFs) constructed from simple aminopyrimidyl derivatives: From oligomer to single neutral zigzag chain and doubly ionic chains

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R ChinaThree low dimensional silver(1)complexes of the formula [Ag(L-1)][Ag(L-1)(CF3SO3)(2)](1), [Ag-2(L-2)(3)(CF3SO3)(2)] (2), and [Ag(L-2)(CF3CO2)](n) (3), where L-1 = 2-amino-4-methoxy-6-methylpyrimidine and L-2 = 2-amino-4,6-dimethoxypyrimidine, have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is a new rarely reported Ag-1 one dimensional (1D)coordination polymer, which consists of independently cat ionic and anionic doubly chains The hydrogen bonds and Ag 0 weak interactions between chains extend 1 into two dimensional (2D) interlayer networks Complex 2 is a simple oligomer and two neighbored oligomers interact to produce a supramolecular dimer through hydrogen bonds, weak Ag N-(amino) interactions and anion-pi interactions Complex 3 displays 1D neutral zigzag chain which is structurally very similar to the 1D cationic one in 1, if neglecting counter anions in the former The adjacent chains in 3 are further interlinked to generate 1D ladder structure via Ag 0 weak interactions and N-H O intermolecular hydrogen bonds. The results reveal that the nature of the Counter anions and organic ligands all has great impact on the structure of the complexes The luminescence properties of the synthesized silver complexes were also investigated in the solid stale at room temperature.National Natural Science Foundation of China 20721001 MSTC 20070815301 Chinese Government Scholarshi

A novel one-dimensional mixed ligands silver(I) coordination polymer containing two different chains

通讯作者地址: Sun, D (通讯作者),Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 地址: 1. Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Fujian, Peoples R China 电子邮件地址: [email protected]; [email protected] mixed-ligand coordination polymer (CP) of the formula {[Ag-3(bmimb)(2) (ndca)(1.5)]center dot H2O}(n) (1) (where bmimb = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene and H(2)ndca = naphthalene-1,4-dicarboxylic acid) was synthesized by reaction of Ag2O and bmimb ligand with H(2)ndca under the ammoniacal condition. It has been structurally characterized by element analysis, IR and X-ray single-crystal diffraction. The bmimb acts as bidentate ligand, and the ndca ligand adopts two different coordination modes in 1, which are mu(4)-eta(1):eta(1):eta(1):eta(1) and mu(2)-eta(1):eta(0):eta(1):eta(0), respectively. Coordination of Ag(I) ions with bmimb and ndca ligands produces two different 1D chains, which is attributed to the different coordination modes of the ndca ligand, indicating the ndca ligand plays an important role in the formation of the diverse 1D chains. The complex 1 exhibits photoluminescent emission in the solid state at room temperature. (C) 2012 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 21021061 21071118 MSTC 2007CB815301 Independent Innovation Foundation of Shandong University 2011GN030 Special Fund for Postdoctoral Innovation Program of Shandong Province 20110100

Synthesis, X-ray structures, and photoluminescence of heterometal trinuclear Hg(II)-Pt(I) and tetranuclear Hg(II)-Pd(I) complexes

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, Dept Chem, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Dept Chem, Xiamen 361005, Peoples R China 2. Xiamen Univ, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] heterometallic trinuclear complex with monovalent platinum consisting of a [Pt2Hg] cluster bridged by two mu(3)-Cl atoms and another tetranuclear complex with monovalent palladium owning the structural core of open cubane-like [Hg2Pd2Cl2I2] framework were synthesized by self-assembly reactions. (C) 2008 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20571062 20721001 National Basic Research Program of China 2007CB81530

Dicarboxylate-controlled three Zn(II) coordination polymers incorporating flexible 1,2-bis(imidazol-1 '-yl)ethane ligand: Syntheses, structures, thermal stabilities and photoluminescent properties

通讯作者地址: Sun, D (通讯作者),Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 地址: 1. Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 电子邮件地址: [email protected]; [email protected] mixed-ligand Zn(II) coordination polymers (CPs) of the formula {[Zn-2(bime)(2)(adiP)(2)]center dot(H2O)(5)}(n) (1), {[Zn(bime)(ipa)]center dot(H2O)3}(n) (2), {[Zn(bime)(tpa)]center dot(H2O)center dot(CH3OH)](n) (3) (bime = 1,2-bis(imidazol-1'-yl)ethane, H(2)adip = adipic acid, H(2)ipa = isophthalic acid and H(2)tpa = terephthalic acid) were synthesized. All CPs have been characterized by element analysis, powder X-ray diffraction (PXRD), IR and X-ray single-crystal diffraction. Complexes 1 and 2 exhibit similar wavy two-dimensional (2D) sheets with 4(4)-sql topology. Compared tot, complex 2 contains a larger window owing to the different conformation of bime ligand. In both 1 and 2, we observed 1D water chain filling in the 44-sql net. In 3, the bime acts as a bidentate ligand and the tpa adopts a mu(2)-eta(1),eta(1) coordinated mode which links the Zn(II) ions to form a 2D 6(3)-hcb net. The results suggest that the dicarboxylates play crucial roles in the formation of the different structures. In addition, the thermal stabilities and the photoluminescence properties of them were also investigated. (C) 2012 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB815301 Independent Innovation Foundation of Shandong University 2011GN030 Special Fund for Post-doctoral Innovation Program of Shandong Province 20110100

Assembly of silver(I) coordination polymers incorporating pyromellitic acid and N-heterocyclic ligands

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] mixed ligands coordination polymers [Ag-4(apym)(2)(pma)center dot(H2O)(2)](n) (1), {[Ag-4(dmapym)(4)(pma)center dot(H2O)(2)]center dot(H2O)(6)](n) (2), [Ag-2(apyz)(2)(H(2)pma)center dot(H2O)(4)](n) (3), {[Ag-4(apyz)(2)(pma)center dot(H2O)(2)]center dot(H2O)(2)}(n) (4) and {Ag-4(NH3)(8)(pma)center dot(H2O)(6)](n) (5) (apym = 2-aminopyrimidine, dmapym = 4, 6-dimethyl-2-aminopyrimidine, apyz = 2-aminopyrazine, H(4)pma = pyromellitic acid) were synthesized and characterized. For 1 and 2, as the substituents change from H to methyl, the dimensions of 1-2 decrease from three-dimension (3D) to one-dimension (ID) due to the steric effect of methyl groups. For 3 and 4, as the ratios of Ag2O/apyz/pma vary from 1:1:1 to 2:1:1. the structure of 3 is a 1D ladder structure built from Ag-apyz double chains and pma anions, while the structure of 4 is a two-dimension (2D) grid. As excess ammonia is added to above four reaction systems, the structure of 5 contains unprecedented {[Ag(NH3)(2)](+)}(n) chains and pma anions. The substituent on the pyrimidyl ring, ratios of reactants, solvent systems and ligand isomers intensively influence the coordination environments of metal ion and the coordination modes of the carboxyl group, and thus determine the structures of the coordination polymers. The photoluminescent properties of 1-5 were also investigated. (C) 2010 Elsevier Ltd. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB81530