【作者】 张婧；

【导师】 吴立新；

【作者基本信息】 吉林大学 ， 物理化学， 2005， 博士

【摘要】 本论文基于合成子和晶体工程的概念,利用氢键、π-π堆积、配位键、静电相互作用以及疏水相互作用等一系列非共价相互作用,以偶氮吡啶（AZP）和二吡啶乙烯（BPE）分别与脂肪二酸、萘二酚、过渡金属盐等作为构筑基元进行超分子组装的晶体工程研究,并总结出相应的晶体构筑规律。此外,我们还利用五羰基氯化铼与希佛碱[2-亚甲基吡啶基-1-氨基萘（L）]和乙腈为原料制备非手性配位化合物,进而自组装成单手性单柱状超分子螺旋结构单晶。本论文共制备了四个系列24 个单晶化合物,表征了它们的结构,主要得到了以下新颖结果: 1. 脂肪酸与AZP 和BPE 构筑的超分子单晶,两个构筑基元在O-H…N/C-H…O 合成子作用下组装成一维条带结构;二维空间上条带间的两个组分采用交替排列还是并肩错位排列取决于组分尺寸的长短。2. 由于羟基的位置不同,萘二酚与AZP 和BPE 在O-H…N 氢键作用下构筑的超分子结构既有环形二聚体组装的条带结构,又有两个组分交替排列构成的扭曲的条带结构,还有按照C₂/c 空间群排列成的“8”字形螺旋结构。3.根据金属的配位几何方式不同,四方平面结构的[CuCl₄]^2-与H₂BPE²⁺在N-H…Cl2 三中心氢键的作用下组装成简单的条带结构;四面体配位结构的[ZnCl₄]^2-和[HgCl₄]^2-与H₂BPE²⁺和H₂AZP²⁺通过N-H…Cl/C-H…Cl合成子组装成单线链、索环链以及环形二聚体,进而组装成波浪层状以及鱼骨状二维堆积结构;FeCl₂和FeCl₃与BPE 和AZP 构筑的晶体,金属部分都是八面体配位的,分别形成下面三种堆积方式:[FeCl₄（H₂O）₂]^2-与H2BPE²⁺通过N-H…Cl/C-H…Cl合成子构筑成环形二聚体;两个[FeCl6]3-与两个发生了质子化和还原了的扭转的H4AZP²⁺ 在N-H…Cl/C-H…Cl 合成子作用下构成环形二聚体; [H₂BPE]₂+[FeCl₃（H₂O）₃]₂和[H₂BPE]²⁺Cl-4正负电荷层交替排列的三明治式结构。4.金属铼与配体希佛碱L 和乙腈以及三个羰基构筑的晶体化合物呈扭曲的八面体几何结构,在C-H…O 氢键作用下组装成单手性柱状螺旋结构。更多还原

【Abstract】 Based on the concepts of supramolecular synthon and crystal engineering, we obtain twenty-four crystals in four series suitable for X-Ray crystallographic diffraction with trans-4,4-azobispyridine (AZP) or 1,2-bis(4-pyridyl)ethylene (BPE) as one of the building blocks. The crystals can be classified to organic molecular, organic-inorganic ionic, organometallic helical structural supermolucules via hydrogen bonding, π-πstacking and coordinated self-organization. The novel structures were solved by direct method, and the refinements were carried out using SHELXTL v. 6.14 program. 1. AZP or BPE with fatty diacid construct crystal engineering via O-H…N/C-H…O synthon. Furthermore, the crystals of p-(4-pyridyl) ethylene toluene with succinic acid and capric acid with BPE were produced for comparison. A conclusion drawn from the investigation of these ten crystals is shown below: (1) In one-dimensional space, AZP or BPE with fatty diacid arrange alternately to tape-like structure. Maleic acid closes to ring, and then aggregates to a dimer with another one via intramolecular O-H…O hydrogen bond. The dimer of maleic acids arrange with BPE alternately to tape-like structure. Two p-(4-pyridyl) ethylene toluene and two capric acids interact via Van der Waals force and hydrophobic interaction worked as a diacid and di-pyridyl base, respectively. (2) In two-dimensional space, when the dimension of diacid comparable to that of di-pyridyl base, interlaced arrangement of the two building blocks in adjacent tape is observed; when the dimension of the former is much longer than that of the latter, the former arrange side-by-side with a little shift as well as the latter between adjacent tapes under the hydrophobic interaction; when the dimension of the former is much shorter than that of the latter, the former shifts left and right along the tape between adjacent tapes forming zig-zag arrangement as well as the latter. (3) In three-dimensional space, π-πinteraction only is observed in the crystals of succinic acid and adipic acid with AZP and BPE. 2. Supramolecular crystals are obtained from BPE with 2,3-dihydroxynaphthalene (2,3-DHN) and 2,7-dihydroxynaphthalene (2,7-DHN) , respectively or AZP with 2,7-DHN as building block via O-H…N synthon. The try to produce crystal of AZP with 2,3-DHN failed. (1) Crystal of BPE with 2,3-DHN form ternary cyclic dimer with the participator of latticed ethanol. The dihedral angle between BPE and 2,3-DHN is 74.1o, and the separation of BPE in a dimer is 3.46? indicating the existence of π-πinteraction. As a result of packing to two-dimensional structure, one BPE (2,3-DHN) couple is encompassed by four 2,3-DHN (BPE) couples. In three-dimensional space, one BPE (2,3-DHN) couple stands above and beneath one 2,3-DHN (BPE) couple. In other word, the first layer overlaps with the third layer exactly. (2) In the crystal of BPE and 2,7-DHN, two building blocks arrange alternately to chain via O-H…N synthon with 50.6o dihedral angle. Under C-H…O intermolecular interaction two building blocks arrange also alternately between adjacent chains to form a layer. Inthree-dimensional space two building blocks arrange alternately between adjacent layers, too, similar with the crystal of BPE wirh 2,3-DHN. (3) Crystal of AZP with 2,7-DHN in C2/c space group form ‘8’shaped helical structure with alternant building blocks via O-H…N synthon. The dihedral angle between AZP and 2,7-DHN neighbour is 12o. As a result of transfer equivalently, there exist π-πinteraction between two pyridyl ring of AZP with 2,7-DHN and another pyridyl, respectively. 3. According to the tendency of protonation and further participate in hydrogen bond, BPE and AZP are used to crystallize with transition metal in acid environment via hydrogen bonding and electrostatic interaction. We obtained ten ionic supramolecular crystals in which metal forms coordinated square planar, tetrahedral and octahedral geometry, respectively. (1) H2BPE2+ with square planar [CuCl4]2-arrange alternately via N-H…Cl2 three-center bifurcate synthon to one-dimensional tape-like structure. Adjacent tapes link to corrugated sheet via α-CH…Cl interaction. Viewed along the direction of tape, every tape is surrounded by six tapes with π-πstacking. (2) Here exhibit three motifs of solid supramolecular structure of H2BPE2+ and H2AZP2+ crystallized with tetrahedral [ZnCl4]2+ and [HgCl4]2+: zig-zag chain induced by N-H…Cl hydrogen bond; grommet chain induced by N-H…Cl/C-H…Cl synthon; cyclic dimer induce by a couple of N-H…Cl/C-H…Cl synthon. Under the influence of tetrahedral geometry of inorganic part the former two are corrugated sheet and the later is herring-bond-like packing structure in two-dimensional space. (3)H2BPE2+ and H2AZP2+ with six-coordinated Fe(II) and Fe(III) form novel supramolecular crystal structure in HCl. H2BPE2+ with [FeCl4(H2O)2]2-form cyclic dimer via N-H…Cl/C-H...Cl synthon which packs to not herring-bond-like structure but zig-zag chain linked by O-H…Ohydrogen bonding. C-H…Cl interchainar interaction contributes to the formation of sheet. Latticed water and HCl solvent cross-link adjacent sheets to three-dimensional structure except for the contribution of π-πstacking. Redox reaction happens when AZP cocrystallizes with FeCl2 in HCl in which azo translates to hydrazine along with Fe(II) to Fe(III). A couple of torsional H4AZP2+ and [FeCl6]3-aggregate to a cyclic dimer with [FeCl4]-in their loop. Crystal of BPE and FeCl3 crystallized in HCl forms the rare sandwich structure of [H2BPE]2+[FeCl3(H2O)3]2 positive sheet and [H2BPE]2+·4Cl-negative sheet alternately. 4. Although this part work is not about AZP or BPE, another Schiff base 2-metheneepridyl-1-aminonaphthalene (L) was used. The chiral construction of complex supramolecular systems is receiving much interest, especially with achiral building units. In this part, we investigated the helical supramolecular structure of an achiral rhenium complex crystal, [Re(CO)3(C16H12N2)(MeCN)].ClO4, which was formed by coordination of Re(CO)5Cl with L and acetonitrile. X-ray diffraction analysis suggests that homohelical column metallosupramolecular architecture results from the array of six-coordinated Re around and along a line: the helical axis in chiral in P 1 21 1 space. There is rare example of constructing helical architectures with both coordinated and hydrogen bonds from achiral units. The helical self-assembly process is induced by the intrastrand interaction and crystal growth. Here, the perchlorate acts as both the counter ion and the bridge linking the neighboring coordinated parts together by weak non-covalent interaction. Furthermore, the two-dimensional arrangement adopts double-edged axe-shaped motif, which is different from the common herringbone or brick-wall pattern in coordination polymers. Our investigationintroduced the special arrangement model into complicated helical architecture, especially homochiral single-colony. In summary, twenty-four crystals’structures have been analyzed and discussed in this thesis, and related crystal engineering character and orderliness have been brought forward which is predictive to the architecture of similar building blocks and synthons.更多还原