Strong electron-acceptor methylviologen dications confined in a 2D inorganic host: synthesis, structural characterization, charge transport and electrochemical properties of (MV)(0.25)V(2)O(5).

The reaction of methylviologen iodide with crystalline V2O5 in the molar ratio of 1 to 3.8 at 100 degrees C in water led to the formation of (MV)0.25V2O5 in quantitative yield. The structure of this organic-inorganic multilayered hybrid compound was determined by single-crystal X-ray crystallography. Strong van der Waals interactions were found between the electron-deficient aromatic organic molecules and the inorganic layers. In the solid state, the compound is a semiconductor due to small polaron hopping and shows novel reversible alkali-ion intercalation/deintercalation via electrochemistry.     

New TGBA series exhibiting a SC*SASA*N* phase sequence

A new series with a chiral tolane core has been synthesized. These materials belong to the optically active series: 3-fluoro-4-[(R) or (S)-1-methylheptyloxy]4'-(4'-alkyloxy-3'-fluorobenzoyloxy)tolanes (nFBTFO₁M₇). For the first time, the helical S_A* phase or TGB_A phase is found in all of the derivatives from heptyloxy to octadecyloxy. The S_A-S_A*-N* phase sequence is observed in several compounds with short chains and the S_C*-S_A-S_A*-N* phase sequence is obtained with the decyloxy derivative. The TGB_A phase has filament or cholesteric textures. The helical pitch of the TGB_A phase is short for the octadecyloxy derivative and is compared with that for different chain lengths as a function of temperature. The layer spacing in the TGB_A phase shows that it is incommensurate with the fully elongated molecular length.     

Optically non-linear organic materials

A large number of non-linear organic materials have been investigated by second-harmonic generation (SHG) in powders. The materials studied include several urea derivatives, sterically perturbed anilines and pyridines, and substituted stilbenes. Several compounds have been found with both a very large second-order non-linearity and a high optical damage threshold. Many compounds, even though known to possess large molecular hyperpolarizabilities, showed no detectable SHG, indicating a centrosymmetric crystal point group. The results are interpreted in terms of bond configuration, charge transfer and crystal structure. The use of good non-linear organic materials in integrated non-linear optics is discussed.     

Improved Parameterization for Combined Isotopomer Analysis of Diatomic Spectra and Its Application to HF and DF

A new way of representing vibration-rotation term values for multiple isotopomers of a given electronic state of a diatomic molecule is presented which resolves problems associated with the way the conventional combined isotopomer expansion represents the atomic mass-dependent JWKB and Born-Oppenheimer breakdown correction terms. Its application to infrared and microwave data for HF and DF yields new Dunham expansion coefficients and Born-Oppenheimer breakdown correction terms for this species. This procedure is implemented in a generally available computer program for fitting to various types of data involving one or several electronic states of multiple isotopomers of a diatomic molecule. Copyright 1999 Academic Press.     

Evaluation of the thermal stability of some nonlinear optical chromophores

Optical data storage is poised to benefit from a new class of advanced polymeric materials engineered to exhibit photorefractivity. Likewise, the transmission and processing of data will also benefit from a related class of materials with electro-optic activity. Organic chromophores are critical constituents of these materials which function due to a change of index of refraction in response to an electric field. However, a number of materials and processing problems remain to be solved before devices incorporating these optically nonlinear chromophores are practical. For example, for electrooptical applications the NLO waveguide should be able to withstand short duration processing temperatures in excess of 300°C and long duration use temperatures of at least 80°C. The requirement for thermochemical stability follows from the need to implement highT _g matrices to provide stability of the orientational or polar order required for long-term device performance and reliability. As a result, the thermal stability of chromophores is now more closely evaluated in addition to their transparency and optical nonlinearity properties. Some chromophore classes, such as the azo dyes studied here, have attractive properties for these applications but further enhancements in overall properties are needed. Identification of the fundamental chemical processes in thermal decomposition of these dyes should lead to introduction of structural changes which provide better stability. Here thermogravimetric analysis (TGA) coupled with mass spectrometry (TGA/MS) is used to provide an assay of thermochemical stability with an added benefit that insight into the mechanisms of thermal decomposition may by identified. In this initial study diaryl substitution of the amine in derivatives of 4-amino-4-nitroazobenzene was observed to greatly enhance thermal stability relative to dialkyl substitution. Substitution of phenyl for alkyl eliminates structural features involved in the most facile degradation mechanism available to the alkyl derivative.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe authors acknowledge contributions by colleagues at IBM including H. Truong and R. Siemens for the thermal analysis. This work was supported by the Air Force Office of Scientific Research and the National Institute of Science and Technology Advanced Technology Program.     

Mesogenic 3,6-bis(4-hydroxyphenyl)-1,2,4,5-tetrazine alkanoate esters

A novel series of 3,6-bis(4-hdroxyphenyl)-1,2,4,5-tetrazine alkanoate esters were synthesized and their mesogenic properties were studied using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The impact of changing the tail-core linkage from alkyl or alkoxy to ester is profound. Compared to the alkyl or alkoxy linkages, the ester linkage reduced mesogenic properties. Short-tailed compounds are non mesogenic (4a-4e), while long-tailed compounds (4f-4r) exhibit nematic phases. Unlike the alkyl or alkoxy tail series, none of the 18 presented esters in this series exhibits a smectic phase.     

Photocyclodehydrofluorination

Mallory‐type photocyclization involves a series of photoreactions of stilbenes, o‐terphenyls and related derivatives, which undergo intramolecular cyclization via dihydrophenanthrene intermediates. In typical Mallory photocyclizations, oxidants are usually needed to produce the final phenanthrene‐containing product. In the research described here, appropriately fluorinated stilbenes and o‐terphenyls undergo ring closure and HF is eliminated. This photocyclodehydrofluorination (PCDHF) reaction is very useful to produce a wide range of selectively fluorinated polynuclear aromatic hydrocarbons that possess a phenanthrene (or heterocyclic analogue of phenanthrene) substructure. These fluorinated products are of great interest in various aspects of the materials science.