Syntheses, Structures and Photoluminescences of Ag-aminopyrimidines Coordination Polymers and Pt-Hg & Pd-Hg Heterometallic Diphosphine Complexes

本论文主要由银离子与氨基嘧啶衍生物配位聚合物的结构调控；Pt-Hg以及Pd-Hg异核金属双膦配合物的元件组装；基于氟化硼络合卤代二吡咯甲川(BODIPY)衍生物为光敏剂的光解水释氢研究等三大部分构成。 以配位键为主、分子间作用力或主客体相互作用为辅的组装方式赋予了配位聚合物具有可调控性强、结构丰富多样、性质可控空间大等特点。基于此特点，配位聚合物在组装过程中易受到合成条件中一些物理、化学因素的影响，因而通过改变反应的溶剂、反应物料比、配体取代基等因素，可得到结构不同的配位聚合物。在此领域中，探索配位聚合物的组装机制仍为研究的焦点之一。论文第一部分主要由氨基嘧啶衍生物与银离子配位聚合物的结构调...The design and assembly of various coordination polymers are currently of great interest due to the richness of their implications in fluorescence, electricity, magnetism and so on. Coordination polymers were mainly assembled with coordination bonds, and some molecular interactions or host-gurst interactions as well. The corresponding bond energies are relatively low, compared to the covalent bond...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：2052006015320

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

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

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

Self-assembly of silver(I) coordination polymers from aminopyrimidyl derivatives and malonate acid: From 1D chain to 2D layer

通讯作者地址: Huang, RB (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, 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] new silver(I) coordination polymers (CPs) of the formula [Ag-2(dmapym)(4)(mal)center dot H2O](n) (1) and [Ag-3(apym)(3)(mal)NO3](n) (2) (dmapym = 2-amino-4,6-dimethylprimidine, apym = 2-aminopyrimidine, H(2)mal = malonate) have been synthesized by reactions of AgNO3 and 2-aminopyrimidyl ligands with malonate under the ammoniacal condition. Both complexes have been characterized by element analysis, IR and single-crystal X-ray diffraction. The monodentate dmapym and tridentate mal ligands link Ag(I) ions to give complex 1 a one-dimensional (1D) H-shaped chain structure. The complex 2 is a two-dimensional (2D) double sheet structure constructed by (4,4) single sheet. Additionally, the hydrogen-bonding and C-H center dot center dot center dot pi interactions also direct the self-assembly of supramolecular architectures. The photoluminescence properties of the 1 and 2 were investigated in the solid state at room temperature. (C) 2010 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Influence of symmetric benzene-polycarboxylate acids on the structures of silver-aminopyrimidyl derivative system

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 China 电子邮件地址: [email protected] novel coordination polymers, [Ag(BTC)(1/3)(ADMP)](n) (1), [Ag(BDC)(1/2)(ADMP)](n) (2) (2-amino-4,6-dimethylpyrimidine = ADMP; H3BTC = 1,3,5-benzenetricarboxylic acid; H2BDC = 1,4-benzenedicarboxylic acid), have been synthesized under the ammoniacal conditions and structurally characterized. In complex 1, H3BTC ligand showing a new coordination mode links silver atoms to generate a two-dimensional (2-D) honeycomb-like structure, which is further linked through ADMP ligands to produce a complicated three-dimensional (3-D) framework. Complex 2 features a 2-D infinite layer framework consisting of binuclear silver clusters, which is further stacked via intermolecular C-methyl-H center dot center dot center dot pi it short contacts and Van der Waals interactions to form a 3-D supramolecular architecture. (C) 2009 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB81530

Influence of dicarboxylic acids on self-assembly process: Syntheses and structural characterization of new Ag(I) complexes derived from mixed ligands

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 China 电子邮件地址: [email protected] the principle of crystal engineering, three new silver metal–organic coordination polymers, [Ag2(L1)2(L2)]·2H2O (1), [Ag2(L1)2(L3)]·H2O (2), [Ag2(L1)2(L4)]·2H2O (3) (L1 = 2-aminopyrimidine, L2 = oxalate anion, L3 = glutarate anion and L4 = 1,4-naphthalenedicarboxylate anion) have been synthesized by solution phase reactions of silver nitrate with various dicarboxylic acids and cooperative heterocyclic 2-aminopyrimidine ligand under the ammoniacal conditions. All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. In complex 1, L1 ligands are coordinated to Ag(I) metal centers in rare tridentate fashions, forming one-dimensional (1-D) ladder-like structure, which is interlinked by L2 anions to generate 2-D pleated molecular sheet. Complex 2 displays an interesting two-dimensional (2-D) tongue-and-groove structure containing a new kind of “T-shaped” unit. Meanwhile, each of 2-D bilayers is interlocked by four adjacent identical motifs to form three-dimensional (3-D) 5-fold interpenetrating conformation with weak Ag···Ag interactions. In complex 3, L1 ligands are coordinated to the Ag(I) ions to form 1-D polymeric chain. And L4 anions, acting as bridging linkers through corresponding μ2-carboxylates, link a pair of Ag(I) atoms from adjacent chains to yield 3-D supramolecular network. The structures of complexes 1–3 which span from 2-D to 3-D networks suggest that dicarboxylate anions play important role in the formation of such coordination architectures.National Natural Science Foundation of China 20721001 973 Project, MSTC 2007CB81530

Another chiral crystal structure of 1-[4-(Dimethylamino)benzylidene]-4-phenylthiosemicarbazide

Another chiral crystal of 1-[4-(dimethylamino)benzylidenel-4-phenylthiosemicarbazide (DMB) was obtained, and its absolute structure was determined by X-ray single crystal diffraction and the solid circular dichroism (CD) spectrum. The crystal belongs to orthorhombic system with space group P2(1)2(1)2(1) and a = 0.7870(2), b = 1. 1560(2), c = 1.6668(3) nm(3), V = 1.5164(5) nm, Z= 4, D-c=1.307 g/cm(3), F(000)=632, mu=0.213 mm(-1), the final R=0.0409 and wR=0.1061 for 2577 observed reflections [I > 2 sigma(I)]. The absolute structure can be determined well with the Flack parameter 0.00(9). The crystal structure and CD spectrum show that an enantiomer of the compound packs into the chiral crystal

Combined Use of Thoracoscopy and Laparoscopy in Total Laryngectomy for Cervical Esophageal Carcinoma

目的探讨胸、腹腔镜联合全喉切除治疗颈段食管的可行性和疗效。方法 2009年1月~2014年7月胸、腹腔镜联合全喉切除治疗33例颈段食管癌。胸腔镜下分离食管、腹腔镜下管胃成形、全喉切除、气管永久造口、胃咽吻合术。结果胸部手术时间40~66 MIn,平均53 MIn;腹部手术时间35~51 MIn,平均44 MIn;颈部手术时间128~150 MIn,平均139 MIn。术中出血量130~270 Ml,平均150 Ml。术后住院时间8~14 d,平均12 d。病理均为鳞状细胞癌,其中高分化2例,中分化19例,中-低分化7例,低分化5例。切缘病理学检查无癌组织残留。31例淋巴结转移。并发症:吻合口漏2例,喉返神经损伤3例,肺部感染6例,胃排空障碍2例,吻合口狭窄1例,无死亡病例。33例随访1个月~5年,术后1、3、5年生存率分别为87.9%、54.5%、45.5%。结论颈段食管癌应采取积极的手术治疗,胃咽吻合术是颈段食管癌切除后较为理想的修复手段。Objective To investigate clinical feasibility and efficacy of combined use of thoracoscopy and laparoscopy in total laryngectomy for cervical esophageal carcinoma.Methods Clinical data of 33 patients with cervical esophageal carcinoma undergoing surgical treatment in our department from January 2009 to July 2014 were analyzed retrospectively.The esophagus was separated under thoracoscopy.And laparoscopic gastroplasty,total laryngectomy,tracheal permanent colostomy,and gastric pharyngeal anastomosis were performed.Results The thoracoscopic operation time was 40- 66 min( mean,53 min),the laparoscopic operation time was 35- 51 min( mean,44 min),and the cervical operation time was 128- 150 min( mean,139 min).The blood loss was 130- 270 ml( mean,150 ml).The postoperative hospital stay was 8- 14 d( mean,12 d).Pathological examinations showed squamous cell carcinoma in all the cases,including 2 cases of highly differentiated carcinoma,19 cases of moderately differentiated carcinoma,7 cases of moderately or lowly differentiated carcinoma,and 5 cases of lowly differentiated carcinoma.No residual cancer was found at cutting edges pathologically.Among the 33 cases,lymph node metastasis was found in 31 cases.Complications included 2 cases of anastomotic fistula,3 cases of recurrent laryngeal nerve injury,6 cases of pulmonary infection,2cases of delayed gastric emptying,and 1 case of anastomotic stenosis.There was no death.All the patients were followed up for 1months to 5 years.The survival rates at 1,3,and 5 postoperative year were 87.9%,54.5%,and 45.5%,respectively.Conclusions Cervical esophageal carcinoma should be surgically treated actively.Gastric pharyngeal anastomosis is an ideal option for the repair of cervical esophageal cancer resection

1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲的另一个手性对映体晶体结构

对-二甲氨基苯甲醛和苯基氨基硫脲缩合反应生成1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲(DMB),产物能从溶液中析出单一手性对映体晶体.用单晶X射线衍射技术测定了它的绝对构型,晶体属正交晶系,P212121空间群,a=0.7870(2)nm,b=1.1560(2)nm,c=1.6668(3)nm,V=1.5164(5)nm3,Z=4,Dc=1.307g/cm3,F(000)=632,μ=0.213mm-1,2557个可观测点[I>2σ(I)]精修的最终残差因子:R=0.0409,wR=0.1061,Flack参数为0.00(9),能够确定绝对构型.化合物的晶体结构和大宗粉末样品的固体圆二色谱表明化合物在结晶过程中发生单一对映体的手性堆积