Disubstituted 1,6-methano[10]annulene derivatives for use in organic light-emitting diodes

Bis(carbazolylphenyl) and bis(diphenylaminophenyl) derivatives of 1,6-methano[10]annulene, which is luminescent material and contains seven-membered rings, are synthesized. The bis(phenylcarbazole) derivative 3 have high melting point and glass transition temperature. Electroluminescence characteristics of organic light-emitting diodes using these methano[10]annulenes were investigated.     

简便合成3,3'-联-1,6-亚甲基桥[10]轮烯

以1,6-二甲酰基环庚三烯为原料通过10π电子环化反应等3步反应制备了3-溴代-1,6-亚甲基桥[10]轮烯, 通过3-溴代-1,6-亚甲基桥[10]轮烯的碱诱导的偶联反应, 简便地合成3,3'-联-1,6-亚甲基桥[10]轮烯, 并用NMR, MS等波谱进行了表征.     

Electronic Structure,Aromaticity and Optical Properties of Dehydro[10]annulene

Dehydro[10]annulene had been prepared experimentally recently, which is considered to be a highly rigid structure with planar configuration. In this paper, the electronic structure and bonding character of dehydro[10]annulene had been studied by means of molecular orbital (MO), density of states (DOS), bond order (BO) and interaction region indicator (IRI) analyses. The delocalization characters of out-of-plane and in-plane π-electrons (π^out- and πⁱⁿ-electrons) of the bond regions were studied by using localized orbital locator (LOL). The anisotropy of the induced current density (AICD), iso-chemical shielding surface (ICSS) and anisotropy of the gauge-including magnetically induced current (GIMIC) were used to investigate the molecular response to external magnetic field, including the induced ring current and the magnetic shielding characteristic. The results showed that the electron delocalization of dehydro[10]annulene is mainly contributed by π^out system. The apparent clockwise current in the π^out system proved that dehydro[10]annulene is π^out aromatic. Finally, the photophysical properties and (hyper)polarizability of dehydro[10]annulene were studied by TD-DFT calculation. The results showed that dehydro[10]annulene has strong local excitation characters. Its (hyper)polarizability decreases with the increase of frequency and has the characteristics of nonlinear anisotropy.     

5，14－二氢－6，8，15，17－四甲基二苯并［b，i］［1，4，8，11］四氮杂［14］轮烯金属配合物的合成和反应性研究

合成了二苯并四氮杂［１４］轮烯金属配合物ＴＭＴＡＡＮｉ（Ⅱ），ＴＭＴＡＡＣｕ（Ⅱ）和ＴＭＴＡＡＶ＝Ｏ，通过ＴＭＴＡＡＭ（Ⅱ）分子中金属离子Ｍ（Ⅱ）对位碳原子上发生酰化反应，获得了十个酰化产物，用元素分析，ＩＲ，ＵＶ，１￣ＨＮＭＲ，（１９）￣ＦＮＭＲ和ＥＰＲ等进行了表征。酰化反应的发生说明了这类金属配合物具有类芳香性，并为改善这类大环金属配合物的光－电性能提供了良好的途径。     

1,6-亚甲基桥[10]轮烯并[3,4-g]-蒽醌衍生物的合成

采用无溶剂合成法,以1,6-亚甲基桥[10]轮烯-3,4-二甲酸酐为原料,Zr OCl2·8H2O/Na Cl为催化剂,于165℃下分别与取代苯经Friedel-Crafts缩合反应合成了4个新型的1,6-亚甲基桥[10]轮烯并[3,4-g]-蒽醌衍生物,其结构经1H NMR,13C NMR,IR,MS和HR-MS表征。     

New dicationic derivatives of dibenzotetraaza[14]annulene: tuning DNA-binding properties

Four new water-soluble derivatives of dibenzotetraaza[14]annulene have been synthesized, bearing meso substituents with different structures and dimensions: 3-(N,N,N-trimethylammonium)propyl, 3-(N-pyridinium-1-yl)propyl, 2-[3-(N,N,N-trimethylammonium)propoxy]benzoyl, and 2-[3-(N-pyridinium-1-yl)propoxy]benzoyl. The crystal structures of 3-(trimethylammonium)propyl and (N,N,N-trimethylammonium)propoxy]benzoyl derivatives were determined by single crystal X-ray analysis. According to the UV-vis titrations, thermal denaturation experiments, and ethidium bromide displacement assays, all compounds presented here interact strongly with double stranded (ct)-DNA. The product equipped with 3-(trimethylammonium)propyl pendant groups and two positive charges interacts with DNA in one dominant binding mode, whereas the other three derivatives revealed more complex mixed-type interactions. The results have been discussed in terms of dimensions, geometry, and electronic properties of the evaluated compounds, on the basis of corresponding crystallographic data.     

二苯并四氮杂[14]轮烯金属配合物电子结构和性质

用量子化学半经验方法和从头算对二苯并四氮杂[14]轮烯（Tmtaa)离子及其金属配合物的电子结构进行了详细的研究.讨论了轮烯金属配合物合成的模板效应及金属离子半径大小对模板效应的影响作用,对其亲电取代反应的活性位置作了相应理论解释.依据理论计算结果指导了轮烯配合物的定向亲电取代反应及新金属配合物的合成尝试,理论计算与实验事实基本一致.Tmtaa-Ni等配合物及其亲电取代反应产物的1HNMR谱、19FNMR谱表明金属配合物中金属离子对位C7、C16上的H原子被取代,与理论计算结果十分一致.     

Controlled direct synthesis of C-mono- and C-disubstituted derivatives of [3,3'-Co(1,2-C2B9H11)2]- with organosilane groups: theoretical calculations compared with experimental results

Mono- and dilithium salts of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-), (1(-)), react with different chlorosilanes (Me(2)SiHCl, Me(2)SiCl(2), Me(3)SiCl and MeSiHCl(2)) with an accurate control of the temperature to give a set of novel C(c)-mono- (C(c) = C(cluster)) and C(c)-disubstituted cobaltabis(dicarbollide) derivatives with silyl functions: [1-SiMe(2)H-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (3(-)); [1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (4(-)); [1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (5(-)); [1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (6(-)) and [1,1'-(SiMe(3))(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (7(-)). In a similar way, the [8,8'-mu-(1',2'-C(6)H(4))-1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(9))(2)](-) (8(-)); [8,8'-mu-(1',2'-C(6)H(4))-1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(9))(2)](-) (9(-)) and [8,8'-mu-(1',2'-C(6)H(4))-1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(9))(1',2'-C(2)B(9)H(10))](-) (10(-)) ions have been prepared from [8,8'-mu-(1',2'-C(6)H(4))-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (2(-)). Thus, depending on the chlorosilane, the temperature and the stoichiometry of nBuLi used, it has been possible to control the number of substituents on the C(c) atoms and the nature of the attached silyl function. All compounds were characterised by NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry; [NMe(4)]-3, [NMe(4)]-4 and [NMe(4)]-7 were successfully isolated in crystalline forms suitable for X-ray diffraction analyses. The 4(-) and 8(-) ions, which contain one bridging -mu-SiMe(2) group between each of the dicarbollide clusters, were unexpectedly obtained from the reaction of the monolithium salts of 1(-) and 2(-), respectively, with Me(2)SiHCl at -78 degrees C in 1,2-dimethoxyethane. This suggests that an intramolecular reaction has taken place, in which the acidic C(c)-H proton reacts with the hydridic Si-H, with subsequent loss of H(2). Some aspects of this reaction have been studied by using DFT calculations and have been compared with experimental results. In addition, DFT theoretical studies at the B3 LYP/6-311G(d,p) level of theory were applied to optimise the geometries of ions 1(-)-10(-) and calculate their relative energies. Results indicate that the racemic mixtures, rac form, are more stable than the meso isomers. A good concordance between theoretical studies and experimental results has been achieved.     

Hydrolysis of tetrafluorosilane under neutral conditions: A quantum chemical study

A density functional quantum chemical study of the first step of SiF₄ hydrolysis under neutral conditions in the presence of one or two H₂O molecules was carried out. The reaction is endothermic and can follow three different pathways that involve the formation of penta-coordinated (pathway A) and hexacoordinated (pathways B and C) intermediates and transition states as the key steps. Pathway B is the most energetically favorable. All three pathways of the hydrolysis reaction lead to a product with formal retention of the configuration of substituents at the silicon atom. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 749–753, May, 2006.     

A Long‐Lived Azafullerenyl Radical Stabilized by Supramolecular Shielding with a [10]Cycloparaphenylene

A major handicap towards the exploitation of radicals is their inherent instability. In the paramagnetic azafullerenyl radical C₅₉N^., the unpaired electron is strongly localized next to the nitrogen atom, which induces dimerization to diamagnetic bis(azafullerene), (C₅₉N)₂. Conventional stabilization by introducing steric hindrance around the radical is inapplicable here because of the concave fullerene geometry. Instead, we developed an innovative radical shielding approach based on supramolecular complexation, exploiting the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling the C₅₉N^. radical. Photoinduced radical generation is increased by a factor of 300. The EPR signal showing characteristic ¹⁴N hyperfine splitting of C₅₉N^.? [10]CPP was traced even after several weeks, which corresponds to a lifetime increase of >10⁸. The proposed approach can be generalized by tuning the diameter of the employed nanobelts, opening new avenues for the design and exploitation of radical fullerenes.     

Sandwich compounds of second-row elements: A quantum chemical study

The structures and stabilities of a number of neutral and charged sandwich-type boron, carbon, and nitrogen compounds designed based on the cyclophane cage and obeying the “electron octet” rule were studied by the B3LYP/6−311+G** density functional method. The possibility of targeted modification of the electronic structures of such compounds by varying the basal or bridging atomic groups was investigated. Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1825–1835, November, 2006.     

F and OH induced monodeprotonation of a lacunar cationic dibenzotetraaza[14]annulene: experimental evidence of tautomerism in a monoanionic macrocycle

A search for selective receptors of anions resulted in a new lacunar cationic derivative of dibenzotetraaza[14]annulene (DBTAA) being synthesized and its crystal structure determined. UV-vis, fluorescence and preliminary ¹H NMR studies of anion binding abilities revealed that under the influence of F⁻ and OH⁻, deprotonation of the macrocycle takes place leading to a zwitterionic species containing a monoanionic DBTAA core and a positively charged quaternized amine nitrogen. The tautomerism of the remaining single NH hydrogen is discussed on the basis of ¹H NMR experiments and DFT calculations.     

Lacunar derivatives of dibenzotetraaza[14]annulene: synthesis and crystal structure of new receptors produced via bis-alkylation of the macrocyclic precursor

The bis(2-hydroxybenzoyl) derivative of dibenzotetraaza[14]annulene was employed as a substrate for producing new lacunar-type receptors. Alkylation of both phenolic OH groups using aliphatic dibromides and ditosylates efficiently leads to the expected bridged products without recourse to a high dilution procedure. Four new dibenzotetraaza[14]annulene-based lacunar receptors, and one unbridged open-chain bis-octoxy analogue have been synthesized. Synthetic procedures, analytical and spectroscopic characterization are reported. Conformations of the macrocyclic rings in the products as well as non-covalent interactions are discussed on the basis of their crystal structures.     

Unique stereochemistry of 3-borabicyclo[3.3.1]nonane derivatives

The conformational equilibrium in solution was examined by NMR spectroscopy for a series of 7-phenyl-3-borabicyclo[3.3.1]nonane derivatives containing various substituents at the boron atom. The structures of these derivatives were studied in the crystalline state (X-ray diffraction analysis) and by quantum-chemical calculations (B3Pw91/6-31G*). The B...Ph transannular interactions corresponding to charge transfer from the system of the phenyl group to the vacant p-orbital of the B atom were demonstrated to be responsible for unique stability of the chair-chair conformation of these derivatives.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1884–1896, September, 2004.     

Synthesis of new derivatives of 1,5,9,13-tetraaza[16]annulene using 2-substituted vinamidinium salts

New 7,15-dibromo-, 7,15-di(bromomethyl)-, and 7,15-di[4-(bromomethyl)phenyl]-1,5,9,13-tetraaza[16]annulene derivatives are synthesized via the condensation reaction of 2-substituted vinamidinium salts [2-substituted 3-(dimethylamino)-N,N-dimethyl-2-propen-1-aminium salts] with 1,8-diaminonaphthalene in acetonitrile/acetic acid. The ultraviolet spectral behavior of these compounds is examined in DMSO.     

A new liquid crystalline derivative of dibenzotetraaza[14]annulene: synthesis, characterization and the preliminary evaluation of mesomorphic properties

A new dibenzotetraaza[14]annulene ligand has been synthesized that contains two 2-hydroxybenzoyl and four 3,7-dimethyloctyloxy peripheral substituents. Its mesomorphic textures were observed by means of a polarizing optical microscopy.     

Synthesis and properties of 1,6-methano[10]annuleno[3,4-c]thiophene and its 1,3-dicyano derivative

New thiophene-annulated 1,6-methano[10]annulene 1 and 2 were synthesized. The anisotropic deshielding effect from the π-electron system, based on the chemical shift values of the bridged methylene protons, is reduced compared with that of 3, and their crystal structures show clear bond alternation.