Structural effects on the electronic properties of extended fused-ring thieno[3,4-b]pyrazine analogues

The synthesis and characterization of the extended thieno[3,4-b]pyrazine analogues acenaphtho[1,2-b]thieno[3,4-e]pyrazine (3a), 3,4-dibromoacenaphtho[1,2-b]thieno[3,4-e]pyrazine (3b), 3-octylacenaphtho[1,2-b]thieno[3,4-e]pyrazine (3c), dibenzo[f,h]thieno[3,4-b]quinoxaline (4), and thieno[3',4':5,6]pyrazino[2,3-f][1,10]phenanthroline (5) are reported. Comparison of structural, electrochemical, and photophysical properties to those of simple thieno[3,4-b]pyrazines are provided in order to provide structure-function relationships within this series of compounds.     

Mechanism of the conversion of inverted CB[6] to CB[6

Inverted cucurbit[n]urils (iCB[n]) form as intermediates during the synthesis of cucurbit[n]urils from glycoluril and formaldehyde in HCl (85 degrees C). Product resubmission experiments establish that the diastereomeric iCB[6] and iCB[7] are kinetic products that are less stable thermodynamically than CB[6] or CB[7] (>2.8 kcal mol(-1)). When iCB[6] or iCB[7] is heated under aqueous acidic conditions, a preference for ring contraction is noted in the formation of CB[5] and CB[6], respectively. Interestingly, under anhydrous acidic conditions ring size is preserved with iCB[6] delivering CB[6] cleanly. To establish the intramolecular nature of the iCB[6] to CB[6] conversion under anhydrous, but not aqueous, acidic conditions we performed crossover experiments involving mixtures of iCB[6] and its (13)C=O labeled isotopomer (13)C(12)-iCB[6]. An unusual diastereomeric CB[6] with a M?bius geometry (13) is proposed as a mechanistic intermediate in the conversion of iCB[6] to CB[6] under anhydrous acidic conditions. The improved mechanistic understanding provided by this study suggests improved routes to CB[n]-type compounds.     

Structure and conformational equilibrium of thiacalix[4]arene by density functional theory

Density functional theory calculations for the structure and conformational equilibrium of thiacalix[4]arene are reported. The conformational equilibrium of thiacalix[4]arene, a heterocalixarene in which the phenol groups are bridged by sulphur atoms is compared to the conformational equilibrium of calix[4]arene. Thiacalix[4]arene conformational energies relative to the cone conformer (ΔE's) are reduced in comparison with calix[4]arene. This conformational change is in qualitative agreement with recent NMR spectroscopy measurements of the conformational equilibrium for a tetraethylether of thiacalix[4]arene in a CDCl₃ solution which indicates an enhanced chemical exchange of thiacalixarene conformers in comparison with similar methylene bridged structures. Density functional theory results for the structure of thiacalix[4]arene are in good agreement with recent X-ray diffraction measurements. The electrostatic potentials in the cone conformers of thiacalix[4]arene and calix[4]arene suggest that their complexation or recognition abilities can be significantly different. Dipole moments of the four thiacalix[4]arene conformers are in the order: cone>1,2-alternate>partial-cone>1,3-alternate.     

Synthesis of Cucurbit[5]uril-Spermine-[2]Rotaxanes

Cucurbit[5]uril and decamethylcucurbit[5]uril are cyclic pentamers built from glycoluril or dimethylglycoluril respectively. Two different experimental methods have been used for the synthesis of the different [2]rotaxanes. The formed rotaxanes are characterized using ¹H-NMR spectroscopy, mass spectrometry and elemental analysis. In contrast to cucurbit[5]uril no [2]rotaxane could be obtained with decamethylcucurbit[5]uril.     

C60与叠氮化合物的单加成反应

本文从实验以及理论研究两方面介绍了C60与叠氧化合物的单加成反应。依照叠氮化合物的不同,C60与叠氮合物的单加成反应可分为烷基叠氮化物与C60的反应,酰基叠氧化物与C60的反应以及苯基叠氮化与C60的反应三类,而反应产物则为C60亚氨基[6,6]闭环衍生物和C60亚氨基[5,6]开环衍生物两类,不同类型的反应具有不同的反应机理,某些C60亚氨基[5,6]开环衍生物可以转化为C60亚氨基[6,6]闭环衍生物。本文还介绍了碳纳米管与叠氮化合物的加成反应。     

Cycloaddition to buckminsterfullerene C60: advancements and future prospects

Investigations on mono-[2+1]-, -[2+2]-, -[2+3]-, -[2+4]-, and polycycloaddition to [60]fullerene are reviewed. The main reagents used in cycloaddition and the reaction mechanisms are surveyed. The possible applications of cycloadducts are considered. The review covers the investigations of the last five years as well as the most important earlier studies.     

A convenient approach to heterocyclic building blocks: synthesis of novel ring systems containing a [5,6]Pyrano[2,3-c]pyrazol-4(1H)-one moiety

Starting from commercially available educts, a straightforward synthetic route to new heterocyclic building blocks is exemplified with the one- or two-step synthesis of tri-, tetra-, or pentacyclic ring systems. Representatives of the following novel ring systems are prepared from 3-methyl-1-phenyl-2-pyrazolin-5-one and the corresponding o-halo-arenecarbonyl chloride using calcium hydroxide in refluxing 1,4-dioxane: pyrimidino[4',5':5,6]pyrano[2,3-c]pyrazol-4(1H)-one, thieno[3',2':5,6]pyrano[2,3c]pyrazol- 4-(1H)-one, thieno[3',4':5,6]pyrano[2,3-c]pyrazol-4(1H)-one, thieno[3',2':4',5']thieno[2',3':5,6]-pyrano[2,3-c]pyrazol-4(1H)-one, [1,3]dioxolo[5',6'][1]benzothieno[2',3':5,6]pyrano-[2,3-c]- pyrazol-4(1H)-one, pyridazino[4',3':5,6]pyrano[2,3-c]pyrazol-4(1H)-one and pyrazolo-[4',3':5',6']pyrido[3',4':5,6]pyrano[2,3-c]pyrazol-4(1H)-one. While the latter two ring systems are directly obtained due to a spontaneous intramolecular substitution reaction, in the other reactions uncyclised 4-aroylpyrazol-5-ols are produced, which are cyclised into the target heterocycles in a subsequent synthetic step (i.e. treatment with NaH in DMF). Detailed NMR spectroscopic investigations ((1)H-, (13)C-, (15)N-) with the obtained compounds were undertaken to unambiguously prove the new structures.     

A new type of ionophore family utilizing the cation-olefinic pi interaction: theoretical study of [n]beltenes

The possible utilization of [n]beltenes as a new family of ionophores, which exhibit a cation-olefinic pi type of interaction in contrast to the cation-aromatic pi type of interaction exhibited by [n]collarenes, has been investigated using both ab initio calculations and molecular dynamic simulations. Like [n]collarenes, n ethene groups are linked by -CH(2)- linkages in the [n]beltenes. Our calculations indicate that these [n]beltenes exhibit strong binding affinities and high selectivity for alkali metal cations ([5]beltene to Li(+), [6]beltene to Na(+), [7]beltene to Na(+) and K(+), [8]beltene to K(+) and Rb(+), and [9]beltene to Cs(+) and Rb(+)). Compared to [n]collarenes, [n]beltenes are expected to have a finer ion selectivity because their cavity sizes can be varied with integral number n, while that of the former can be varied with an even number n. Suitable substituents could be employed to enhance both the binding and specificity of various sizes of [n]beltenes to different cations, as well as to increase the solubility.     

Hydrogen activation on Mo-based sulfide catalysts,a periodic DFT study

Hydrogen adsorption on Mo[bond]S, Co[bond]Mo[bond]S, and Ni[bond]Mo[bond]S (10 1 macro 0) surfaces has been modeled by means of periodic DFT calculations taking into account the gaseous surrounding of these catalysts in working conditions. On the stable Mo[bond]S surface, only six-fold coordinated Mo cations are present, whereas substitution by Co or Ni leads to the creation of stable coordinatively unsaturated sites. On the stable MoS(2) surface, hydrogen dissociation is always endothermic and presents a high activation barrier. On Co[bond]Mo[bond]S surfaces, the ability to dissociate H(2) depends on the nature of the metal atom and the sulfur coordination environment. As an adsorption center, Co strongly favors molecular hydrogen activation as compared to the Mo atoms. Co also increases the ability of its sulfur atom ligands to bind hydrogen. Investigation of surface acidity using ammonia as a probe molecule confirms the crucial role of sulfur basicity on hydrogen activation on these surfaces. As a result, Co[bond]Mo[bond]S surfaces present Co[bond]S sites for which the dissociation of hydrogen is exothermic and weakly activated. On Ni[bond]Mo[bond]S surfaces, Ni[bond]S pairs are not stable and do not provide for an efficient way for hydrogen activation. These theoretical results are in good agreement with recent experimental studies of H(2)[bond]D(2) exchange reactions.     

Gold nanoparticles in organic capsules: a supramolecular assembly of gold nanoparticles and cucurbituril

Gold nanoparticles (相似文献   

Local aromaticity of [n]acenes, [n]phenacenes, and [n]helicenes (n = 1-9)

The local aromaticity of the six-membered rings in three series of benzenoid compounds, namely, the [n]acenes, [n]phenacenes, and [n]helicenes for n = 1-9, has been assessed by means of three probes of local aromaticity based on structural, magnetic, and electron delocalization properties. For [n]acenes our analysis shows that the more reactive inner rings are more aromatic than the outer rings. For [n]phenacenes, all indicators of aromaticity show that the external rings are the most aromatic. From the external to the central ring, the local aromaticity varies in a damped alternate way. The trends for the [n]helicene series are the same as those found for [n]phenacenes. Despite the departure from planarity in [n]helicenes, only a very slight loss of aromaticity is detected in [n]helicenes as compared to the corresponding [n]phenacenes. Finally, because of magnetic couplings between superimposed six-membered rings in the higher members of the [n]helicenes series, we have demonstrated that the NICS indicator of aromaticity artificially increases the local aromaticity of their most external rings.     

Synthesis of benzo[g]quinoline derivatives

In the condensation of 1, 2, 3, 4-tetrahydro-4-oxobenzo[g]quinollne with ammonia, which leads to the formation of 4-aminobenzo[g]quinoline, the by-products are benzo[g]quinoline (V) and 1, 2, 3, 4-tetrahydrobenzo]quinoline (VI), which are also obtained from 1, 2, 3, 4-tetrahydro-4hydroxybenzo[g]quinoline by its dehydration and the subsequent disproportionation of the dihydrobenzo[g]quinoline formed.For communication II, see [1].     

Effects of fluorine on the structures and energetics of the propynyl and propargyl radicals and their anions

[reaction: see text] The adiabatic electron affinity (EA(ad)) of the CH(3)-C[triple bond]C(*) radical [experiment = 2.718 +/- 0.008 eV] and the gas-phase basicity of the CH(3)-C[triple bond]C:(-) anion [experiment = 373.4 +/- 2 kcal/mol] have been compared with those of their fluorine derivatives. The latter are studied using theoretical methods. It is found that there are large effects on the electron affinities and gas-phase basicities as the H atoms of the alpha-CH(3) group in the propynyl system are substituted by F atoms. The predicted electron affinities are 3.31 eV (FCH(2)-C[triple bond]C(*)), 3.86 eV (F(2)CH-C[triple bond]C(*)), and 4.24 eV (F(3)C-C[triple bond]C(*)), and the predicted gas-phase basicities of the fluorocarbanion derivatives are 366.4 kcal/mol (FCH(2)-C[triple bond]C:(-)), 356.6 kcal/mol (F(2)CH-C[triple bond]C:(-)), and 349.8 kcal/mol (F(3)C-C[triple bond]C:(-)). It is concluded that the electron affinities of fluoropropynyl radicals increase and the gas-phase basicities decrease as F atoms sequentially replace H atoms of the alpha-CH(3) in the propynyl system. The propargyl radicals, lower in energy than the isomeric propynyl radicals, are also examined and their electron affinities are predicted to be 0.98 eV ((*)CH(2)-C[triple bond]CH), 1.18 eV ((*)CFH-C[triple bond]CH), 1.32 eV ((*)CF(2)-C[triple bond] CH), 1.71 eV ((*)CH(2)-C[triple bond]CF), 2.05 eV ((*)CFH-C[triple bond]CF), and 2.23 eV ((*)CF(2)-C[triple bond]CF).     

Mass spectra of 1,2-alkylenedioxy-substituted and related benzofurazans and benzofuroxans: differentiation between linear and angular isomers.

The electron ionization (EI) mass spectra of [1,3]-dioxolo-, 6, 7-dihydro-[1,4]-dioxino-, 7,8-dihydro-6H-[1,4]dioxepino-, 6,7,8, 9-tetrahydro[1,4]dioxocino-, 7,8,9,10-tetrahydro-6H-[1,4]dioxonino- and 6,7,8,9,10,11-hexahydro[1,4]dioxecino[2,3-f]-2,1, 3-benzoxadiazoles (benzofurazans) and the corresponding 1-oxides (benzofuroxans), all linear isomers, are reported. Also reported are the EI mass spectra of the corresponding angular isomers, [1, 3]dioxolo-, 7,8-dihydro[1,4]dioxino-, 8,9-dihydro-7H-[1,4]dioxepino-, 7,8,9,10-tetrahydro[1,4]dioxocino-, 8,9,10,11-tetrahydro-7H-[1, 4]dioxonino-, 7,8,9,10,11,12-hexahydro[1,4]dioxecino[2,3-e]-2,1, 3-benzoxadiazoles and the corresponding 1-oxides. The relative abundance of the fragment ion of m/z 80 is characteristically enhanced in the spectra of the angular derivatives compared to the spectra of the linear counterparts. Collisionally activated decomposition studies show that it is structurally identical whether derived from the benzofurazans or the benzofuroxans. The relative abundance of the m/z 80 ion serves to distinguish between linear and angular isomeric pairs. In addition, the fragment ion at m/z 80 also serves to differentiate between the pairs of isomers, analogous to linear and angular, of six acyclic methoxy- and methoxymethyl-substituted benzofurazans and their corresponding benzofuroxans.     

Low-valent group-13 chemistry. Theoretical investigation of the structures and relative stabilities of donor-acceptor complexes R(3)E[bond]E'R' and their isomers R(2)E[bond]E'RR'

The results of quantum chemical calculations at the gradient-corrected density functional theory (DFT) level with the B3LYP functional of the donor-acceptor complexes R(3)E[bond]E'R' and their isomers R(2)E[bond]E'RR', where E, E' = B[bond]Tl and R, R' = H, Cl, or CH(3), are reported. The theoretically predicted energy differences between the donor-acceptor form R(3)E[bond]E'R' and the classical isomer R(2)E[bond]E'RR' and the bond dissociation energies of the E[bond]E' bonds are given. The results are discussed in order to show which factors stabilize the isomers R(3)E[bond]E'R'. There is no simple correlation of the nature of the group-13 elements E, E' and the substituents R, R' with the stability of the complexes. The isomers R(3)E[bond]'R' come stabilized by pi donor groups R', while the substituents R may either be sigma- or pi-bonded groups. Calculations of Cl(3)B[bond]BR' [R' = Cl, cyclopentadienyl (Cp), or Cp*] indicate that the Cp* group has a particularly strong effect on the complex form. The calculations show that the experimentally known complex Cl(3)B[bond]BCp* is the strongest bonded donor-acceptor complex of main-group elements that has been synthesized until now. The theoretically predicted B[bond]B bond energy is D(o) = 50.6 kcal/mol. However, the calculations indicate that it should also be possible to isolate donor-acceptor complexes R(3)E[bond]E'R' where R' is a sigma-bonded bulky substituent. Possible candidates that are suggested for synthetic work are the borane complexes (C(6)F(5))(3)B[bond]E'R' and (t)Bu(3)B[bond]E'R' (E' = Al[bond]Tl) and the alane complexes Cl(3)Al[bond]E'R' (E' = Ga[bond]Tl).     

气态[HPro（C1）]＋和[Sac]-相互作用及质子转移机制的理论研究

质子化功能离子液体在许多重要领域具有潜在的应用价值,然而人们对其相互作用模式、质子转移行为等方面的认识尚不清晰．本文利用DFT／B3LYP和MP2方法,以脯氨酸阳离子[HPro]＋、脯氨酸甲酯阳离子[HProC1]＋和糖精阴离子[Sac]=组成的质子化离子液体（PILs）为研究对象,探讨气态离子对、分子对、双聚体团簇中的结构单元及其作用模式．利用过渡态和内禀反应坐标（IRC）理论研究气态[HPro]＋[Sac]-和[HProCl]＋[Sac]-中的质子转移反应,AIM（atomsinmolecules）理论分析给出氢键相互作用本质等．计算结果表明,气态单聚体中氢转移能垒很小,体系中存在离子对和分子对的动态平衡．质子转移发生后,体系内部基本作用单元改变,作用强度下降,形成分子对的相互作用能量远远小于离子对的相互作用能量．双聚体团簇计算说明体系中没有质子转移反应发生,在[HPro]2＋[Sac]2-中相互作用的基本结构单元为离子、分子和两性离子,酯化后双聚体[HProC1]2＋[Sac]2-中全部为阴阳离子相互作用．质子转移反应、两性离子和酯化作用等的深入研究对于理解功能化PILs的性质、结构因素及其应用具有一定的实际意义．     

Aza and deaza analogs of purine nucleosides (review)

Methods for the preparation of aza and deaza analogs of purine nucleosides, viz., nucleosides of imidazo[4,5-d]-v-triazines, imidazo[4,5-b]pyridines, and imidazo[4,5-c]pyridines, and their properties are described. References to the synthesis of nucleosides of imidazo[4,5-d]pyridazines, imidazo[4,5-c]pyridazines, and imidazo[4,5-b]pyrazines are also given.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 147–161, February, 1981.     

Probing ruthenium-acetylide bonding interactions: synthesis, electrochemistry, and spectroscopic studies of acetylide-ruthenium complexes supported by tetradentate macrocyclic amine and diphosphine ligands

The synthesis and spectroscopic properties of trans-[RuL4(C[triple bond]CAr)2] (L4 = two 1,2-bis(dimethylphosphino)ethane, (dmpe)2; 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, 16-TMC; 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane, N2O2) are described. Investigations into the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the [(-)C[triple bond]C(C6H4C[triple bond]C)(n-1)Ph] and [(-)C[triple bond]C(C6H4)(n-1)Ph] (n = 1-3) series upon the electronic and electrochemical characteristics of trans-[RuL4(C[triple bond]CAr)2](0/+) are presented. DFT and TD-DFT calculations have been performed on trans-[Ru(L')4(C[triple bond]CAr)2](0/+) (L' = PH3 and NH3) to examine the metal-acetylide pi-interaction and the nature of the associated electronic transition(s). It was observed that (1) the relationship between the transition energy and 1/n for trans-[Ru(dmpe)2{C[triple bond]C(C6H4C[triple bond]C)(n-1)Ph}2] (n = 1-3) is linear, and (2) the sum of the d(pi)(Ru(II)) --> pi*(C[triple bond]CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2] and the pi(C[triple bond]CAr) --> d(pi)(Ru(III)) LMCT energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2]+ corresponds to the intraligand pi pi* absorption energy for trans-[Ru(16-TMC or N2O2)(C[triple bond]CAr)2]. The crystal structure of trans-[Ru(dmpe)2{C[triple bond]C(C6H4C[triple bond]C)2Ph}2] shows that the two edges of the molecule are separated by 41.7 A. The electrochemical and spectroscopic properties of these complexes can be systematically tuned by modifying L4 and Ar to give E(1/2) values for oxidation of trans-[RuL4(C[triple bond]CAr)2] that span over 870 mV and lambda(max) values of trans-[RuL4(C[triple bond]CAr)2] that range from 19,230 to 31,750 cm(-1). The overall experimental findings suggest that the pi-back-bonding interaction in trans-[RuL4(C[triple bond]CAr)2] is weak and the [RuL4] moiety in these molecules may be considered to be playing a "dopant" role in a linear rigid pi-conjugated rod.     

Rim-differentiated pillar[5]arenes

Pillar[5]arenes, designed and prepared by Ogoshi et al. in 2008 initially, refer to fifth classical macrocyclics. Among a wide range of pillar[5]arenes, rim-differentiated pillar[5]arenes containing five identical substituents on one rim and five different identical groups on the other rims are considered the most noteworthy type of pillar[5]arenes. As compared with the perfunctionalized pillar[5]arene, the self-assembly properties of rim-differentiated pillar[5]arenes have more varieties. On the other hand, in comparison with other types of pillar[5]arenes, the rim-differentiated pillar[5]arenes exhibit a more rigid symmetrical structure. In the present review, the synthetic methods, host-guest interactions, self-assembly properties and applications of rim-differentiated pillar[5]arenes are summarized. Hopefully, this review will be conducive to researchers in macrocyclic supramolecular chemistry.     

A concise synthesis of all four possible benzo[4,5]furopyridines via palladium-mediated reactions

[reaction: see text] By taking advantage of the alpha- and gamma-activation of chloropyridines as well as palladium-mediated reactions, all four possible benzo[4,5]furopyridine tricyclic heterocycles, benzo[4,5]furo[2,3-b]pyridine, benzo[4,5]furo[2,3-c]pyridine, benzo[4,5]furo[3,2-c]pyridine, and benzo[4,5]furo[3,2-b]pyridine, are efficiently synthesized from 2-chloro-3-iodopyridine, 3-chloro-4-stannylpyridine, 4-chloro-3-iodopyridine, and 2-chloro-3-hydroxypyridine, respectively.