EXISTENCE OF NATURAL FREQUENCIES OF SYSTEMS WITH ARTIFICIAL RESTRAINTS AND THEIR CONVERGENCE IN ASYMPTOTIC MODELLING

A major limitation of the Rayleigh-Ritz method for determining the natural frequencies of a system is the need to choose admissible functions that do not violate the geometric constraints of that system (Courant 1943 Bulletin of the American Mathematical Society49, 1-23). Several researchers have attempted to overcome this problem by asymptotically modelling the rigid constraints with artificial (imaginary) restraints of very large stiffness (Courant 1943Bulletin of the American Mathematical Society49 , 1-23; Warburton and Edney 1984 Journal of Sound and Vibration95, 537-552; Gorman 1989 Journal of Applied Mechanics56, 893-899; Kim et al. 1990 Journal of Sound and Vibration143, 379-394; Yuan and Dickinson 1992 Journal of Sound and Vibration153, 203-216; Yuan and Dickinson 1992 Journal of Sound and Vibration159, 39-55; Cheng and Nicolas 1992 Journal of Sound and Vibration155, 231-247; Yuan and Dickinson 1994Computers and Structures53 , 327-334; Lee and Ng 1994 Applied Acoustics42, 151-163; Amabili and Garziera 1999 Journal of Sound and Vibration224, 519-539; Amabili and Garziera 2000 Journal of Fluids and Structures14, 669-690). While the numerical results thus obtained for the systems considered in the literature were in close agreement with exact values for the natural frequencies corresponding to the first few modes, sample calculations show that the error introduced by the asymptotic modelling increases with mode number and therefore to obtain accurate results for higher modes the magnitude of stiffness should also be increased. In any event, the error due to the asymptotic modelling would remain uncertain, except when the correct frequency values are known. However, the use of artificial restraints with negative stiffness, a new concept which was introduced in a recent publication (Ilanko and Dickinson 1999 Journal of Sound and Vibration219, 370-378) paves the way for estimating the error due to asymptotic modelling. This is possible since in this work, the Rayleigh-Ritz frequencies of the constrained system were found to be bracketed by the frequencies of the asymptotic models with positive and negative restraints. However, the use of artificial restraints with negative stiffness has raised some important questions: would a system with a large negative restraint become unstable, and if so what is the guarantee that the frequencies of the asymptotic model would converge to that of the constrained system? This paper is the result of the author's attempt to answer these questions and gives a proof of existence of natural frequencies for systems with artificial restraints (springs) having positive or negative stiffness coefficients, and their convergence towards constrained systems. Based on Rayleigh's theorem of separation, it has been shown that a vibratory system obtained by the addition of h restraints to an n -degree-of-freedom (d.o.f.) system, where h<n, will have at least (n÷h) natural frequencies and modes and that as the magnitude of the stiffness of the added restraints becomes very large, these (n÷h) natural frequencies will converge to the (n÷h) natural frequencies of a constrained system in which the displacements restrained by the springs are effectively constrained.     

IDENTIFICATION OF DAMPING: PART 3, SYMMETRY-PRESERVING METHODS

In two recent papers (Adhikari and Woodhouse 2001 Journal of Sound and Vibration243, 43-61; 63-88), methods were proposed to identify viscous and non-viscous damping models for vibrating systems using measured complex frequencies and mode shapes. In many cases, the identified damping matrix becomes asymmetric, a non-physical result. Methods are presented here to identify damping models which preserve symmetry of the system. Both viscous and non-viscous models are considered. The procedure is based on a constrained error minimization approach and uses only experimentally identified complex modes and complex natural frequencies together with, for the non-viscous model, the mass matrix of the system. The methods are illustrated by numerical examples.     

NORMAL MODES OF A NON-LINEAR CLAMPED-CLAMPED BEAM

Non-linear modal analysis approach based on invariant manifold method proposed earlier by Shaw and Pierre (Journal of Sound and Vibration164, 85-124) is utilized here to obtain the non-linear normal modes of a clamped-clamped beam for large amplitude displacements. The results obtained for the fundamental normal mode are compared with the corresponding reported experimental and theoretical studies. The effects of modal coupling are examined in greater detail. The limitation of the present method for analyzing non-linear behavior is highlighted.     

GEOMETRICALLY NON-LINEAR FREE VIBRATION OF FULLY CLAMPED SYMMETRICALLY LAMINATED RECTANGULAR COMPOSITE PLATES

The geometrically non-linear free vibration of thin composite laminated plates is investigated by using a theoretical model based on Hamilton's principle and spectral analysis previously applied to obtain the non-linear mode shapes and resonance frequencies of thin straight structures, such as beams, plates and shells (Benamar et al. 1991Journal of Sound and Vibration149 , 179-195; 1993, 164, 295-316; 1990 Proceedings of the Fourth International Conference on Recent Advances in Structural Dynamics, Southampton; Moussaoui et al. 2000 Journal of Sound and Vibration232, 917-943 [1-4]). The von Kármán non-linear strain-displacement relationships have been employed. In the formulation, the transverse displacement W of the plate mid-plane has been taken into account and the in-plane displacements U and V have been neglected in the non-linear strain energy expressions. This assumption, quite often made in the literature has been adopted in reference [2] and (El Kadiri et al. 1999 Journal of Sound and Vibration228, 333-358 [5]), in the isotropic case and has been mentioned here because the results obtained have been found to be in very good agreement with those based on the hierarchical finite element method (HFEM). In a previous study, it was assumed, based on the analogy with the isotropic case, that the fundamental carbon fibre reinforced plastic (CFRP) plate non-linear mode shape could be well estimated, by using nine plate functions, obtained as products of clamped-clamped beam functions in the x and y directions, symmetric in both the length U001and width directions [3]. In the present work, a convergence study has been performed and has shown that, although such an assumption may yield a good estimate for the non-linear resonance frequency, 18 plate functions should be taken into account instead of nine in the first non-linear mode shape and associated bending stress patterns calculations. This allows the anisotropy induced by the fibre orientations to be taken into account. Results are given for the fundamental mode of fully clamped CFRP rectangular plates, for various plate aspect ratios and vibration amplitudes. The non-linear mode shows a higher bending stress near the clamps at large deflection, compared with that predicted by linear theory. Some experimental measurements are presented which are in good qualitative agreement with the theory.     

IMPROVEMENT OF THE SEMI-ANALYTICAL METHOD, FOR DETERMINING THE GEOMETRICALLY NON-LINEAR RESPONSE OF THIN STRAIGHT STRUCTURES. PART I: APPLICATION TO CLAMPED-CLAMPED AND SIMPLY SUPPORTED-CLAMPED BEAMS

In a previous series of papers (Benamar 1990 Ph.D. Thesis, University of Southampton; Benamaret al. 1991 Journal of Sound and Vibration149, 179-195;164, 399-424 [1-3]) a general model based on Hamilton's principle and spectral analysis has been developed for non-linear free vibrations occurring at large displacement amplitudes of fully clamped beams and rectangular homogeneous and composite plates. The results obtained with this model corresponding to the first non-linear mode shape of a clamped-clamped (CC) beam and to the first non-linear mode shape of a CC plate are in good agreement with those obtained in previous experimental studies (Benamaret al. 1991 Journal of Sound and Vibration 149, 179-195;164, 399-424 [2, 3]). More recently, this model has been re-derived (Azar et al. 1999 Journal of Sound and Vibration224, 377-395; submitted [4, 5]) using spectral analysis, Lagrange's equations and the harmonic balance method, and applied to obtain the non-linear steady state forced periodic response of simply supported (SS), CC, and simply supported-clamped (SSC) beams. The practical application of this approach to engineering problems necessitates the use of appropriate software in each case or use of published tables of data, obtained from numerical solution of the non-linear algebraic system, corresponding to each problem. The present work was an attempt to develop a more practical simple “multi-mode theory” based on the linearization of the non-linear algebraic equations, written on the modal basis, in the neighbourhood of each resonance. The purpose was to derive simple formulae, which are easy to use, for engineering purposes. In this paper, two models are proposed. The first is concerned with displacement amplitudes of vibrationW_max /H, obtained at the beam centre, up to about 0·7 times the beam thickness and the second may be used for higher amplitudes W_max/H up to about 1·5 times the beam thickness. This new approach has been successfully used in the free vibration case to the first, second and third non-linear modes shapes of CC beams and to the first non-linear mode shape of a CSS beam. It has also been applied to obtain the non-linear steady state periodic forced response of CC and CSS beams, excited harmonically with concentrated and distributed forces.     

BIFURCATIONS AND CHAOS OF AN IMMERSED CANTILEVER BEAM IN A FLUID AND CARRYING AN INTERMEDIATE MASS

The concern of this work is the local stability and period-doubling bifurcations of the response to a transverse harmonic excitation of a slender cantilever beam partially immersed in a fluid and carrying an intermediate lumped mass. The unimodal form of the non-linear dynamic model describing the beam-mass in-plane large-amplitude flexural vibration, which accounts for axial inertia, non-linear curvature and inextensibility condition, developed in Al-Qaisia et al. (2000Shock and Vibration7 , 179-194), is analyzed and studied for the resonance responses of the first three modes of vibration, using two-term harmonic balance method. Then a consistent second order stability analysis of the associated linearized variational equation is carried out using approximate methods to predict the zones of symmetry breaking leading to period-doubling bifurcation and chaos on the resonance response curves. The results of the present work are verified for selected physical system parameters by numerical simulations using methods of the qualitative theory, and good agreement was obtained between the analytical and numerical results. Also, analytical prediction of the period-doubling bifurcation and chaos boundaries obtained using a period-doubling bifurcation criterion proposed in Al-Qaisia and Hamdan (2001 Journal of Sound and Vibration244, 453-479) are compared with those of computer simulations. In addition, results of the effect of fluid density, fluid depth, mass ratio, mass position and damping on the period-doubling bifurcation diagrams are studies and presented.     

Experimental identification of viscous damping in linear vibration

This paper is concerned with the experimental evaluation of the performance of viscous damping identification methods in linear vibration theory. Both existing and some new methods proposed by the present authors [A.S. Phani, J. Woodhouse, Viscous damping identification in linear vibration, Journal of Sound and Vibration 303 (3–5) (2007) 475–500] are applied to experimental data measured on two test structures: a coupled three cantilever beam with moderate modal overlap and a free–free beam with low modal overlap. The performance of each method is quantified and compared based on three norms and the best methods are identified. The role of complex modes in damping identification from vibration measurements is critically assessed.     

TOWARDS DEEP AND SIMPLE UNDERSTANDING OF THE TRANSCENDENTAL EIGENPROBLEM OF STRUCTURAL VIBRATIONS

When using exact methods for undamped free vibration problems the generalized linear eigenvalue problem (K−ω²M) D=0 of approximate methods, e.g., finite elements, is replaced by the transcendental eigenvalue problem K (ω) D=0. Here ω is the circular frequency; D is the displacement amplitude vector; M and K are the mass and static stiffness matrices; and K (ω) is the dynamic stiffness matrix, with coefficients which include trigonometric and hyperbolic functions involving ω and mass because elements (for example, bars or beams) are analyzed exactly by solving their governing differential equations. The natural frequencies of this transcendental eigenvalue problem are generally found by the Wittrick-Williams algorithm which gives the number of natural frequencies below ω_t, a trial value of ω, as ∑J_m+s{K (ω_t)} wheres {} denotes the readily computed sign count property of K (ω) and the summation is over the clamped-clamped natural frequencies of all elements of the structure. Understanding the alternative solution forms of the transcendental eigenvalue problem is important both to accelerate convergence to natural frequencies, e.g., by plotting ∣K (ω)∣, and to improve the mode calculations, which lack the complete reliability of natural frequencies obtained by using the Wittrick-Williams algorithm. The three solution forms are: ∣K (ω)∣=0; D=0 with ∣K (ω)∣→∞; and ∣K (ω)∣≠0 with D≠0. The literature covers the first two forms thoroughly but the third form has been almost totally ignored. Therefore, it is now examined thoroughly, principally by analytical studies of simple bar structures and also by confirmatory numerical results for a rigidly jointed plane frame. Although structures are unlikely to have exactly the properties giving this form, it needs to be understood, particularly because ill-conditioning can occur for structures approximating those for which it occurs.     

EXPERIMENTAL STUDY ON THE VORTEX-INDUCED VIBRATION OF TOWED PIPES

We experimentally attempted to understand the vibration characteristics of a flexible pipe excited by vortex shedding. This has been extensively studied in the previous decades (for example, see Sarpkaya 1979 Journal of Applied Mechanics46, 241-258; Price et al. 1989 Eighth International Conference on Offshore Mechanics and Arctic Engineering, The Hague-March 19 -23, 447-454; Yoerger et al. 1991 Journal of Offshore Mechanics and Arctic Engineering, Transaction of Engineers113, 117-127; Grosenbaugh et al. 1991Journal of Offshore Mechanics and Arctic Engineering, Transaction of Engineers113 , 199-204; Brika and Laneville 1992 Journal of Fluid Mechanics250, 481-508; Chakrabarti et al. 1993 Ocean Engineering20, 135-162; Jong 1983 Ph.D. Dissertation, Department of Ocean Engineering, M. I. T.; Kimet al. 1986 Journal of Energy Resources Technology, Transactions of American Society of Mechanical Engineers108, 77-83). However, there are still areas that need more study. One of them is the relation between spatial characteristics of a flow-induced vibrating pipe, such as its length, the distribution of wave number, and frequency responses. A non-linear mechanism between the responses of in-line and cross-flow directions is also an area of interest, if the pipe is relatively long so that structural modal density is reasonably high. In order to investigate such areas, two kinds of instrumented pipe were designed. The instrumented pipes, of which the lengths are equally 6 m, are wound with rubber and silicon tape in different ways, having different vortex-shedding conditions. One has uniform cross-section of diameter of 26·7 mm, and the other has equally spaced four sub-sections, which are composed of different diameters of 75·9, 61·1, 45·6 and 26·7 mm. Both pipes are towed in a water tank (200 m×16 m×7 m) so that they experienced different vortex-shedding excitations. Various measures were obtained from the towing experiment, including frequency responses, the time-domain tracing of in-line and cross-flow responses, and Wigner-Ville distributions. The experimental results analyzed by using these measures exhibit several valuable features. One of them is that the natural frequencies and their corresponding strain mode shapes dominate the strain response of the uniform pipe. However for those of non-uniform pipe, the responses are more likely local and many modes participate in it.     

Dispersion induced splitting of the collective mode spectrum in A-phase of superfluid He

The whole collective mode spectrum in A-phase of superfluid ³He with dispersion corrections is calculated. The degeneracy of clapping-modes depends on the direction of the collective mode momentum k with respect to the vector l (mutual orbital moment of Cooper pairs), namely: the mode degeneracy remains the same as in case of zero momentum k for k∥l only. For any other directions there is a three-fold splitting of these modes, which reaches maximum for k⊥l. The obtained results means that new interesting features can be observed in ultrasound experiments in axial-phase: the change of the number of peaks in ultrasound absorption into clapping-mode. Single peak, observed for these modes in axial-phase by Ling et al. [R. Ling, W. Wojtanowski, J. Saunders, E.R. Dobbs, J. Low Temp. Phys. 78 (1990) 187] will split into three peaks under change the ultrasound direction with respect to the vector l.     

A SEMI-ANALYTICAL APPROACH TO THE NON-LINEAR DYNAMIC RESPONSE PROBLEM OF BEAMS AT LARGE VIBRATION AMPLITUDES, PART II: MULTIMODE APPROACH TO THE STEADY STATE FORCED PERIODIC RESPONSE

The semi-analytical approach to the non-linear dynamic response of beams based on multimode analysis has been presented in Part I of this series of papers (Azrar et al., 1999 Journal of Sound and Vibration224, 183-207 [1]). The mathematical formulation of the problem and single mode analysis have been studied. The objective of this paper is to take advantage of applying this semi-analytical approach to the large amplitude forced vibrations of beams. Various types of excitation forces such as harmonic distributed and concentrated loads are considered. The governing equation of motion is obtained and can be considered as a multi-dimensional form of the Duffing equation. Using the harmonic balance method, the equation of motion is converted into non-linear algebraic form. Techniques of solution based on iterative-incremental procedures are presented. The non-linear frequency and the non-linear modes are determined at large amplitudes of vibration. The basic function contribution coefficients to the displacement response for various beam boundary conditions are calculated. The percentage of participation for each mode in the response is presented in order to appraise the relation to higher modes contributing to the solution. Also, the percentage contributions of the higher modes to the bending moment near to the clamps are given, in order to determine accurately the error introduced in the non-linear bending stress estimated by different approximations. Solutions obtained in the jump phenomena region have been determined by a careful selection of the initial iteration at each frequency. The non-linear deflection shapes in various regions of the solution, the corresponding axial force ratios and the bending moments are presented in order to follow the behaviour of the beam at large vibration amplitudes. The numerical results obtained here for the non-linear forced response are compared with those from the linear theory, with available non-linear results, based on various approaches, and with the single mode analysis.     

Luminescence and crystal-field fitting of two optical isomeric complexes of europium

FT-IR and Raman vibrational spectra and electronic emission spectra have been recorded for enantiomers of europium complexes with DBM: dibenzoylmethanate 1,2, and TTFA: 2-thenoyltrifluoroacetonate 3,4, employing the chiral ligands L_SS(+)- and L_RR(-)-4,5-pinene bipyridine. Contrary to the previously published X-ray data, where geometrical differences were stated to occur for particular enantiomers, the vibrational (and the emission) spectra of the individual optical isomers of a complex are not distinguishable. Using excitation into the Eu³⁺⁵D₂ multiplet term, the emission intensity is weak from ⁵D₁, whereas a complex structure is observed for the ⁵D₀→⁷F_J transitions. Features in the vibronic sidebands exhibit similar derived vibrational energies to those observed in the Raman spectra. Fittings of 25 4f⁶ crystal-field energy levels of 2 and 4 have been attempted with some approximations concerning the local Eu³⁺ environments. The ⁵D₀ emission lifetimes are monoexponential and are 0.5 (1,2) and 0.9 ms (3,4) at room temperature.     

Morphic effects — III. Effects of an external magnetic field on the long wavelength optical phonons

The changes in the frequencies of the k ≈ 0 optical vibration modes on the application of a static, external magnetic field to a non-magnetic crystal are determined to first order in the field strength. Second order effects are equivalent to the effects of an electric field in second order and they are not considered here. It is shown that the frequency of a nondegenerate mode is not altered to first order in the magnetic field. In the case of the noncubic crystal structures it is found that the magnetic field must have a component along the axis of highest symmetry in order that the doubly degenerate modes at k ≈ 0 have their degeneracy lifted. In the case of the cubic structures a magnetic field applied in any direction can completely split the degeneracy of modes which are triply degenerate at k ≈ 0. Expressions are given for the field induced changes in the normal mode frequencies. The modes whose frequencies are shifted are found to be right or left circularly polarized. A brief discussion is given of spatial dispersion effects, that is, splitting of the mode degeneracy linear in the phonon wave-vector. Finally, a review of the symmetry aspects of acoustical activity and Faraday effects of acoustical phonons is presented.     

A Theoretical Study of MgNC and MgCN in the X?Σ Electronic State

The MgNC radical was the first Mg-containing species to be observed in interstellar space. This fact has stimulated considerable spectroscopic interest in this molecule, and in its isomer MgCN, but nevertheless the only rotationally resolved spectroscopic data presently available for X?²Σ⁺ MgNC comprise the rotational spectrum (K. Kawaguchi et al., 1993, Astrophys. J.406, L39-L42; K. Ishii et al., 1993, Astrophys. J.410, L43-L44; M. A. Anderson and L. M. Ziurys, 1994, Chem. Phys. Lett.231, 164-170; E. Kagi et al., 1996, J. Chem. Phys.104, 1263-1267; E. Kagi and K. Kawaguchi, J. Mol. Spectrosc. 2000, 199, 309-310) together with a few vibronic bands, all originating in the vibronic ground state and belonging to the òΠ←X?²Σ⁺ electronic transition (R. R. Wright and T. A. Miller, 1999, J. Mol. Spectrosc.194, 219-228). For MgCN, only the rotational spectrum in the vibrational ground state is known (M. A. Anderson, T. C. Steimle, and L. M. Ziurys, 1994, Astrophys. J.429, L41-L44). We report here potential energy surfaces calculated by the Averaged Coupled-Pair Functional (ACPF) method with TZ3P+f (Mg), TZ2P+f(N,C) basis sets including core-valence correlation due to the Mg 2s and 2p electrons. The ab initio results are used for determining the standard spectroscopic constants of X?²Σ⁺ MgNC and MgCN. Also, we report variational calculations of the rotation-vibration energies, and variational simulations of the lowest rotation-vibration bands, carried out with the MORBID program system (P. Jensen, 1988, J. Mol. Spectrosc.128, 478-501). We hope that our theoretical results will encourage and facilitate further characterization of X?²Σ⁺ MgNC and MgCN by high-resolution spectroscopy.     

Synthesis of 2,3-dimorpholino-6-aminoquinoxaline derivatives and application to a new intramolecular fluorescent probe

Two fluorescent monomers having a quinoxaline skeleton, N-(2,3-dimorpholinoquinoxalin-6-yl)acrylamide (QxA) and N-(1-(2,3-dimorpholinoquinoxalin-6-ylamino)prop-2-yl)methacrylamide (QxAlaMA), were synthesized. Thermo-responsive copolymers of N-isopropylacrylamide (NIPAM) and a small amount of a fluorescent monomer were synthesized and their fluorescence properties investigated. The fluorescent monomers showed intense solvatochromism in their fluorescence. The wavelength at the maximum fluorescence intensity of the QxAlaMA-labeled PNIPAM dramatically blue-shifted and the fluorescence intensity of the QxA-labeled PNIPAM significantly increased around the transition temperature. It was found that these fluorescent dyes can sense and report the thermo-responsive behavior of the PNIPAM in water. Both QxAlaMA and QxA were demonstrated to be applicable to new intramolecular fluorescent probes.     

Isomerization and fluorescence characteristics of sterically hindered azobenzene derivatives

We report synthesis and isomerization behaviors of sterically hindered azobenzene derivatives (1 and 2) with decyloxy and hydroxy groups, respectively, and their fluorescence enhancement under UV light irradiation characterized by means of absorption and fluorescence spectroscopy measurements. Upon irradiation of as-prepared solution (1) with UV light (∼200 mJ/cm²) a cis-rich photostationary state was reached. Obviously different from 2 showing very fast thermal cis-to-trans isomerization within 2 min, slow cis-to-trans thermal back isomerization of 1 with a long alkyl chain at ambient temperature was observed on the time scale of weeks. In contrast to no striking changes in absorption and fluorescence spectra of compound 2, the azobenzene 1 showed green fluorescence upon prolonged irradiation with UV light (about 3-8 J/cm² exposure doses), although both the initial trans-rich and cis-rich states of azobenzene molecules were not fluorescent in solution. The stability of fluorescence efficiency caused by drying and redissolving processes was examined.     

Synthesis, characterization and optical limiting effect of nickel complexes of multi-sulfur 1,2-dithiolene

Three nickel complexes with a new multi-sulfur 1,2-dithiolene ligand, (n-Bu₄N)[Ni(cddt)₂] 1, (Ph₄P)[Ni(cddt)₂] 2 and [Ni(cddt)₂] 3 (cddt=4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3-dithiolate), have been synthesized and characterized by electrochemical measurements, IR, EPR and UV-Vis-NIR spectroscopies. The crystal structure of complex 2 is determined. Their optical nonlinearities are measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm and all exhibit NLO absorptive abilities. Complexes 1 and 2 both exhibit effective self-defocusing performance (n₂=−5.81×10⁻¹⁰ esu for 1 and −4.51×10⁻¹⁰ esu for 2). The optical limiting (OL) effects were observed with nanosecond and picosecond laser pulses. The OL capability of complex 3 is superior to C₆₀ at the same experimental condition in ns measurements.     

Photophysical characteristics of 4,4′-bis(N-carbazolyl)tolan derivatives and their application in organic light emitting diodes

4,4′-bis(N-carbazolyl)tolan (BCT) and 4,4′-bis[N-(3,6-di-t-butyl)carbazolyl]tolan (BCT-t-Bu) were synthesized as π-expanded analogs of 4,4′-bis(N-carbazolyl)biphenyl. Their photophysical characteristics both in solution and films were thoroughly investigated. Interestingly, the phosphorescence spectrum of BCT was significantly medium-dependent, and the emission maximum was red-shifted by 131 nm from 489 nm in solution at 77 K to 620 nm in a deposited film at 5 K, suggesting the presence of strong intermolecular interactions in the film. BCT and BCT-t-Bu were found to be useful as host materials for fluorescence-based organic light emitting diodes (OLEDs). However, their low triplet energy levels in films negated their potential to act as hosts in phosphorescence-based OLEDs.     

Organic radical molecular solids based on [(TCNQ)n] (n=1 or 2): Syntheses, crystal structures, magnetic properties and DFT analyses

Four molecular solids consisting of the 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical and benzylpyridinium or benzylquinolinium derivatives with molar ratios of 1:1 (1-3) and 2:1 (4) have been prepared and characterized. In the crystals of 1 and 3, TCNQ⁻ monoanions and the corresponding cations form segregated stacks, which are regular in 1 but irregular in 3. Instead of segregated stacks, TCNQ⁻ monoanions in 2 form isolated π-dimers. In the crystals of 4, two crystallographic independent TCNQ species possess almost equal fractional negative charge (ca. −0.5). Two types of TCNQ species form a tetrad, these tetrads make a TCNQ stack with the pattern …BAAB…BAAB… along the crystallographic a-b direction. The magnetisms for 1-4 can be simply explained by the formation of singlet spin state. A broken symmetry approach in a density functional theory framework at the ub3lyp/6-31 g level was used to calculate the magnetic exchange constants in 1-4. The results qualitatively demonstrate the observed magnetic properties.     

Three green luminescent cadmium complexes containing 8-aminoquinoline ligands: Syntheses, crystal structures, emission spectra and DFT calculations

Three complexes, Cd(8-aminoql)₂×₂ (8-aminoql=8-aminoquinoline; X⁻=ClO₄⁻, SCN⁻, 1 and 2, respectively) and Cd(8-aminoql)(N₃)₂ (3), were synthesized and structurally characterized. For each complex, the Cd²⁺ ion exhibits distorted octahedral coordination geometry. Two 8-aminoquinoline molecules and two counter-anions are coordinated to the Cd²⁺ center to form a mononuclear species with two trans-ClO₄⁻ anions for 1, while two SCN⁻ anions adopt a cis-configuration for 2. The intermolecular H-bonding interactions between the -NH₂ groups and the O atom (1) and the S atom (2) result in the formation of a 2-D layered structure. In the crystal of 3, the N₃⁻ anions bridging the neighboring Cd(8-aminoql)²⁺ units form a 1-D coordination polymer. The three complexes emit green luminescence. The emission bands possess a broad asymmetric feature, which can be assigned to L′LCT transitions based on DFT and TDDFT calculations.