柏木醇与酚类化合物包合现象的研究

分子包合物是主体分子和客体分子相互作用组成的复合物(又称为主客体化合物),具有独自的晶形和熔点。利用主体分子形成的空间特点可有效地识别客体分子,用于同分异构体的分离、光学拆分及立体选择性化学反应。 柏木醇(1)是由雪松中提取出来的天然产物,其构型式见文献[4],熔点为87℃、[α]_D为+9.31°(CHCl_3)。(1)可与苯酚(2)、邻甲酚(3)、间甲酚(4)和对甲酚(5)形成分子包合物。     

反式9, 10-二氢-9, 10-二苯基-9, 10-菲二醇包结性能的研究

合成了一种具有螯形结构的反式-9, 10-二氢-9, 10-二苯基-9,10-菲二醇(1)作为主体分子。它能与许多有机小分子化合物, 诸如DMF, DMSO, 吡啶, 哌啶, 喹啉, 异喹啉等形成包结化合物。本文还报道了这些包结化合物的IR, 粉末XRD的表征, 用^1H NMR谱测定了它们的分子摩尔比。DMF包结物的单晶四圆X衍射结果表明主体分子1与客体分子形成的包结物为配位笼状包合物。     

六元瓜环与二氯化-1,8-二(2-苯并咪唑基)辛烷的自组装模式

采用¹H NMR、 荧光光谱和紫外吸收光谱法考察了主体六元瓜环与合成客体二氯化-1,8-二(2-苯并咪唑基)辛烷的自组装模式. 结果表明, 六元瓜环能与二氯化-1,8-二(2-苯并咪唑基)辛烷发生相互作用, 瓜环包结客体分子的苯并咪唑基团, 烷基链置于瓜环端口外侧. 自组装模式与主客体的摩尔比密切相关. 当主客体的摩尔比为1:1时, 1个瓜环包结客体分子的一端苯并咪唑基团形成棒槌形的包结配合物; 当主客体的摩尔比为2:1时, 2个瓜环分别包结客体分子的两端苯并咪唑基团形成哑铃型的主客体包结配合物.     

六元瓜环与含双苯并咪唑功能基烷烃的自组装模式及晶体结构

以含有双苯并咪唑功能基的烷烃化合物二氯化-1,4-二(2,2’-苯并咪唑基)丁烷(SBB)为客体,普通六元瓜环(Q[6])为主体,利用1H NMR技术、荧光发射光谱和X-单晶衍射实验等考察了主客体的自组装模式.1 H NMR技术结果显示,当主客体的比例为1:1时,在水溶液中,1个Q[6]包结1个客体分子的一端苯并咪唑基团;在结晶固态条件下,X-单晶衍射实验测试结果是Q[6]包结客体分子的烷基链.荧光发射光谱表明,当主客体比例为2:1时,2个Q[6]分别包结1个客体分子的两端苯并咪唑基团形成哑铃型的实体配合物。     

超分子体系中轴－轮状D.D.主体分子的立体异构现象

组装了轴一轮状主体分子1,1,6,6-四基乙－2,4－二炔-1,6二醇(1)与天然主物异补骨脂素(2)。茴香醚(3)形成的两种超分子异构体的包结物晶体,它们的主客体分子摩尔比分别为1：2和2：1单晶X射线衍射分析了游离主体分子以及超分子包结物晶体的结构,结果表明在主客体分子摩尔比1：2的晶体中,主体分子与异补骨脂素形成氢键,主体分子采取对位交叉式构象;在主客体分子摩尔比为2：1的晶体中,主体分子这间形成氢键,主体分子采取邻位交叉式构,主体分子所取的构象取决于客体分子的性质,当客体分子为氢键好的受体时,可与主体分子生成1：2的包结物;当客体分子为氢键差的受体时,生成2：1有包结物,本文还对三种晶体是的主体分子的立体构苯环两面角,C(1)和C(6)所连基团的夹角和能量变化规律进行了比较和分析。     

无机分析用有机试剂的分析功能团的研究——Ⅱ.锑试剂的分析功能团的研究

作者研究了三个类型的 Sb~Ⅲ“试剂:(1)含有酸性基的化合物,(2)所谓 Caille-viel 试剂,(3)含有两个邻位酚基的化合物。由结果得出,(1)和(2)两个类型的试剂的灵敏度不高,并且不能用变动结构式来提高灵敏度。第(3)类试剂,即含有两邻位酚基的化合物显然是最有希望的 Sb~Ⅲ试剂。它们的反应是相当灵敏的。作者制备了几类有色化合物,其中二羟基荧光黄和三羟基金色素是满意的 Sb~Ⅲ试剂。     

邻巯基苯酚过渡金属配合物研究和(Et_4N)[Mn(OC_6H_4SSC_6H_4O_2)]的晶体结构

本文以邻巯基苯酚(mpH_2)为配体合成了五个第一周期过渡金属化合物(Ph_4P)[V_3(mp)_6]1,(Et_4N)[Mn(mp-mp)_2]2,(Et_4N)_2[Fe_2(mp)_4]3,(Et_4N)_2[Co(mp)(mpH)]_2 4及(Et_4N)_2[Ni_2(mp)_2(Hmp)_2]5.本文着重报道化合物2的晶体和分子结构.由于邻巯基苯酚配位形式的多样性,诸化合物中金属的配位构型各不相同,但又有其规律性.     

螯形主体分子的设计、包结性能及其在细辛挥发油 有效成分选择分离中的应用

设计了两种新的具有螯形骨架的主体分子反式-1,2-二苯基-1,2-苊二醇(1)和顺式-1,2-二(1'-萘基)-1,2-苊二醇(2),主体(1),(2)可与许多有机小分子化合物形成配位包合物。用IR和粉末XRD表征了主体分子(1)和(2)的包结物,用^1NMR测定了包结物的主客体分子摩尔比：(1)·DMF(1:2),(1)·DMSO(1:2),(1)·THF(1:2),(1)·二氧六环(1:1),(1)·吡啶(1:1),(2)·DMF(1:1)和(2)·DMSO(1:1)。单晶X射线衍射分析了包结物的晶体结构,(1)·DMF：空间群Pnaa,a=0.9377(1)nm,b=1.4351(1)nm,c=4.0463(3)nm;(1)·DMSO：空间群Pbcn,a=1.6278(1)nm,b=1.0751(1)nm,c=1.4980(1)nm;(2)·DMF：P2~1/n,a=0.9796(1)nm,b=1.2377(1)nm,c=2.2344(3)nm,β=93.02(1)°;游离主体(1)：空间群P1,a=1.0461(1)nm,b=1.1213(1)nm,c=1.5496(1)nm,α=81.74(1)°,β=75.71(1)°,γ=89.00(1)°;分析了主体分子的刚性和柔韧性对包结性能的影响。并研究了主体分子(1)选择分离细辛挥发油,将顺甲基异丁香酚从挥发油中分离出来。     

螯形主体分子的设计、包结性能及其在细辛挥发油 有效成分选择分离中的应用

设计了两种新的具有螯形骨架的主体分子反式-1,2-二苯基-1,2-苊二醇(1)和顺式-1,2-二(1'-萘基)-1,2-苊二醇(2),主体(1),(2)可与许多有机小分子化合物形成配位包合物。用IR和粉末XRD表征了主体分子(1)和(2)的包结物,用^1NMR测定了包结物的主客体分子摩尔比：(1)·DMF(1:2),(1)·DMSO(1:2),(1)·THF(1:2),(1)·二氧六环(1:1),(1)·吡啶(1:1),(2)·DMF(1:1)和(2)·DMSO(1:1)。单晶X射线衍射分析了包结物的晶体结构,(1)·DMF：空间群Pnaa,a=0.9377(1)nm,b=1.4351(1)nm,c=4.0463(3)nm;(1)·DMSO：空间群Pbcn,a=1.6278(1)nm,b=1.0751(1)nm,c=1.4980(1)nm;(2)·DMF：P2~1/n,a=0.9796(1)nm,b=1.2377(1)nm,c=2.2344(3)nm,β=93.02(1)°;游离主体(1)：空间群P1,a=1.0461(1)nm,b=1.1213(1)nm,c=1.5496(1)nm,α=81.74(1)°,β=75.71(1)°,γ=89.00(1)°;分析了主体分子的刚性和柔韧性对包结性能的影响。并研究了主体分子(1)选择分离细辛挥发油,将顺甲基异丁香酚从挥发油中分离出来。     

两种三蝶烯型分子钳的合成及其络合性能研究（英文）

本文合成了两种含有三蝶烯单元的分子钳1和2,通过1H NMR、13C NMR、质谱、元素分析以及X射线单晶衍射等手段确证了化合物的结构。通过核磁滴定法以及ESI-MS法研究了化合物1和2在溶液中与7种缺电子客体的络合行为,结果表明:1)主客体之间的络合是按照摩尔比1∶1进行的;2)两种主体的配位能力12;3)缺电子程度大的客体与主体络合能力强。利用ORTEP 1.076理论计算模拟主客体络合行为,结果表明非共价键相互作用在主客体形成夹心络合物的过程中起着重要作用。     

Guest-induced supramolecular isomerism in inclusion complexes of T-shaped host 4,4-bis(4'-hydroxyphenyl)cyclohexanone

The T-shaped host molecule 4,4-bis(4'-hydroxyphenyl)cyclohexanone (1) has an equatorial phenol group and a cyclohexanone group along the arms and an axial phenol ring as the stem. The equatorial phenyl ring adopts a "shut" or "open" conformation, like a windowpane, depending on the size of the guest (phenol or o/m-cresol), for the rectangular voids of the hydrogen-bonded ladder host framework. The adaptable cavity of host 1 expands to 11x15-18 A through the inclusion of water with the larger cresol and halophenol guests (o-cresol, m-cresol, o-chlorophenol, and m-bromophenol) compared with a size of 10x13 A for phenol and aniline inclusion. The ladder host framework of 1 is chiral (P2(1)) with phenol, whereas the inclusion of isosteric o- and m-fluorophenol results in a novel polar brick-wall assembly (7x11 A voids) as a result of auxiliary C-H...F interactions. The conformational flexibility of strong O-H...O hydrogen-bonding groups (host 1, phenol guest), the role of guest size (phenol versus cresol), and weak but specific intermolecular interactions (herringbone T-motif, C-H...F interactions) drive the crystallization of T-host 1 towards 1D ladder and 2D brick-wall structures, that is, supramolecular isomerism. Host 1 exhibits selectivity for the inclusion of aniline in preference to phenol as confirmed by X-ray diffraction, 1H NMR spectroscopy, and thermogravimetry-infrared (TG-IR) analysis. The T(onset) value (140 degrees C) of aniline in the TGA is higher than those of phenol and the higher-boiling cresol guests (T(onset)=90-110 degrees C) because the former structure has more O-H...N/N-H...O hydrogen bonds than the clathrate of 1 with phenol which has O-H...O hydrogen bonds. Guest-binding selectivity for same-sized phenol/aniline molecules as a result of differences in hydrogen-bonding motifs is a notable property of host 1. Host-guest clathrates of 1 provide an example of spontaneous chirality evolution during crystallization and a two-in-one host-guest crystal (phenol and aniline), and show how weak C-H...F interactions (o- and m-fluorophenol) can change the molecular arrangement in strongly hydrogen-bonded crystal structures.     

Synthesis of novel cyclodextrin derivatives by aromatic spacer insertion and their inclusion ability

Novel cyclic host molecules were synthesized by the insertion of three types of aromatic spacers into the skeleton of permethylated α-cyclodextrin. These host molecules formed a 1:1 complex with sodium 3- and 4-nitrobenzenesulfonates (3- and 4-NBS), and sodium 2,4-dinitrobenzenesulfonate (DNBS) in D₂O/CD₃OD (4:1) solution. The type of spacer inserted remarkably affected the inclusion ability of the hosts toward DNBS. The p-xylylene-inserted CDs showed greater inclusion ability toward DNBS than permethylated α- and β-CDs.     

New Exo-Functional Cyclophane Hosts. Synthesis and Crystal Structures of Inclusion Compounds

The new cyclophane type host compounds 1–3, containing rigid aromatic units and two exo-topic carboxylic acid functions, have been synthesized. Crystalline solvent inclusions, involving the dicarboxylic acid hosts and their corresponding ester intermediates 6 (a–c), namely 1·DMSO (1:4), 2·pyridine (1:3), 3·pyridine (1:4), 6a·pyridine (1:2) and 6a·benzene (1:2), have been prepared and studied using X-ray diffraction on single-crystals. Moreover, X-ray structure analyses of the solvent-free crystals of the 6 (a, b) intermediates were also carried out for comparison. Co-crystals of the carboxylic hosts 1–3 contained H-bonded 1:2 host-guest associates as building blocks, together with additional space-filling guests, whereas only loosely bounded space-filling solvent molecules were found in the two solid inclusion compounds of the 6a cyclophane ester host. In addition to the mentioned conventional H-bond interactions between carboxylic hosts and their guests, the crystal structures proved to be held together by relatively weak C–H…O bonds besides the ordinary van der Waals' interactions. Packing relations, and the effects of structural variations, guest molecules and anisotropic packing forces on the conformation of the semi-rigid cylcophane ring have been discussed and compared in seven crystal structures.     

Polymer complexes. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [(11)+(12)] in the paper and in mononuclear polymer complexes (1)-(5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX2 and KPtCl4 in the presence of N-heterocyclic base consisting of polymer complexes (9)+(10), and in monouclear compounds (6)-(8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds (13)+(14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.     

Structure-activity relationships in the acceleration of a hetero Diels-Alder reaction by metalloporphyrin hosts

At 0.33 mM in dichloromethane at 25 degrees C the cyclic metalloporphyrin hosts 5, 7, 8, and 10 accelerate 12-fold, 260-fold, 1130-fold, and 250-fold, respectively, the reaction of 1 and 2 and also bind the product 3 very strongly. These observations combined with previously measured results with hosts 6, 9, and 11 allowed us to explore the influence of host geometry changes on acceleration rates and product binding over a wide range of host molecules of different size, ranging from extremely tightly strapped to very relaxed. To estimate the Zn-Zn distance in the transition-state complex, we carried out quantum mechanical calculations (at the HF/6-31G level) for the transition state to form 3. The structure-activity relationships found for hosts 5-11, along with the structural features calculated for the transition-state structure between 1 and 2 and previously crystallographically observed for product-free hosts and for a host.product complex,(4) suggest that both host preorganization as well as host flexibility are key features leading to high acceleration rates and product binding and that it is the delicate balance between the two structural features that leads to maximum efficiency.     

Helical tubulate inclusion compounds

Abstract

The inclusion properties of the first helical tubuland diol hosts 1–5 have been surveyed and are reported. Bicyclic diol 1 forms helical tubulate inclusion compounds with most small solvent molecules, but with certain phenols hydrogen bonded co-crystalline materials are produced instead. Diol 2 yields helical tubulates with larger guest molecules, but if smaller solvents are used then an alternative host system is obtained. This has the guests trapped in ellipsoidal cavities located along constricted canals and is termed the ellipsoidal clathrate type. In some cases both inclusion types can be produced from 2 by varying the experimental conditions. The free volume present in the helical tubuland lattices of 3 and 5 is insufficient for guest inclusion. Diol 4 has the largest void space and can form inclusion compounds with large molecules such as ferrocene and squalene. X-ray crystal structures of representative examples of these compounds are discussed.     

Cationic Re(V) oxo complexes with poly(pyrazolyl)borates: synthesis, characterization, and stability

Cationic Re(V) oxo compounds of the type [ReO(OSiMe3)(eta 2-B(pz)4)(L)2]X [X = Cl, L = 4-(NMe2)C5H4N (1), 1-Meimz (1-methylimidazole; 2), 1/2 dmpe (1,2-bis(dimethylphosphino)ethane; 3), py (4a); X = I, L = py (4b)] can be prepared by reacting trans-[ReO2(eta 2-B(pz)4)(L)2] with XSiMe3. In solution, cations 1-4 are reactive species, and those with unidentate nitrogen donor ligands (1, 2, and 4) rearrange into the neutral derivatives [ReO(Cl)(OSiMe3)(eta 2-B(pz)4)(L)] [L = py (5), 4-(NMe2)C5H4N (6), 1-Meimz (7)], which are also reported herein. Compounds 1-3 and 5-7 have been fully characterized by the usual spectroscopic techniques, which in some cases includes X-ray crystallographic analysis (3, 6, and 7). Compound 3 crystallizes from CH2Cl2/n-hexane as yellow crystals with one molecule of CH2Cl2 solvent, and compounds 6 and 7 crystallize from THF/n-hexane as violet and red crystals, respectively, with one molecule of THF solvent in the case of 6. Crystallographic data: 3, orthorhombic space group Pn2(1)a, a = 11.311(2) A, b = 19.135(2) A, c = 15.443(2) A, V = 3342.4(8) A3, Z = 4; 6, triclinic space group P1, a = 8.7179(11) A, b = 12.5724(8) A, c = 17.750(2) A, alpha = 70.454(7) degrees, beta = 77.935(9) degrees, gamma = 77.129(8) degrees, V = 1768.1(3) A3, Z = 2; 7, monoclinic space group P2(1)/c, a = 16.356(2) A, b = 20.384(3) A, c = 17.360(3) A, beta = 106.971(12) degrees, V = 5535.8(14) A3, Z = 8.     

Silicon Analogues of Triarylmethanol Hosts. Inclusion Properties and Host–guest Structures: A Comparative Study

The simple triarylmethanol hosts, 2 and 4, and their silicon analogues, 1 and 3, have been studied for comparison of the formation of crystalline inclusion compounds. Clathrate formation experiments showed that replacement of the carbinol C atoms in 2 and 4 by Si atoms to give 1 and 3 resulted in a distinct increase of the capability to form inclusion compounds with organic guests, in particular with alcohols. Moreover, the naphthyl derivatives are much more efficient than the phenyl species, irrespective of the carbinol and silanol features. In order to investigate and compare the guest recognition modes and packing relations of hosts 1–4 in their crystalline inclusion compounds, 11 selected co-crystals, namely 1·DMSO (2:1), 3·EtOH (1:1), 3· i-PrOH (1:1), 3·acetone (1:1), 3·DMSO (1:1), 3·THF (1:1), 3·piperidine (1:1), 4·acetone (1:1), 4·DMSO (1:1), 4·1,4-dioxane (1:1) and 4·benzene (1:1), were studied by X-ray diffraction from single crystals. The survey contains additional 11 crystal structures from the literature and provides a detailed discussion of isostructurality relationships.Supplementary Data relevant to this publication have been deposited with the Cambridge Crystallographic Data Centre as supplementary publications nos. CCDC 274780–274790.     

Three-coordinate organoboron compounds BAr2R (Ar = mesityl, R = 7-azaindolyl- or 2,2'-dipyridylamino-functionalized aryl or thienyl) for electroluminescent devices and supramolecular assembly

Eight novel three-coordinate boron compounds with the general formula BAr(2)L, in which Ar is mesityl and L is a 7-azaindolyl- or a 2,2'-dipyridylamino-functionalized aryl or thienyl ligand, have been synthesized by Suzuki coupling, Ullmann condensation methods, or simple substitution reactions (L = p-(2,2'-dipyridylamino)phenyl, 1; p-(2,2'-dipyridylamino)biphenyl, 2; p-(7-azaindolyl)phenyl, 3; p-(7-azaindolyl)biphenyl, 4; 3,5-bis(2,2'-dipyridylamino)phenyl, 5; 3,5-bis(7-azaindolyl)phenyl, 6; p-[3,5-bis(2,2'-dipyridylamino)phenyl]phenyl, 7; 5-[p-(2,2'-dipyridylamino)phenyl]-2-thienyl, 8). The structures of 1, 3, and 5-7 have been determined by X-ray diffraction analyses. These new boron compounds are bright blue emitters. Electroluminescent devices using compound 2 or 8 as the emitter and the electron-transport layer have been successfully fabricated. Molecular orbital calculations (Gaussian 98) have established that the blue emission of compounds 1-8 originates from charge transfer between the pi orbital of the ligand L and the p(pi) orbital of the boron center. The ability of these boron compounds to bind to metal centers to form supramolecular assemblies was demonstrated by treatment of compound 2 with Zn(O(2)CCF(3))(2), which generated a 1:1 chelate complex [2.Zn(O(2)CCF(3))(2)] (10), and also by treatment of compound 4 with AgNO(3), yielding a 2:1 coordination compound [(4)(2).Ag(NO(3))] (11). In the solid state, compounds 10 and 11 form interesting head-to-head and tail-to-tail extended structures that host solvent molecules such as benzene.