1H, 2H and 13C NMR spectra and molecular dynamics of some solid alkylene-aromatic polyesters

Molecular dynamics of some mesomorphic main–chain alkylene–aromatic polyesters have been investigated by means of NMR spectra of various nuclei over a wide temperature range. In solid polymers regions of different molecular mobilities coexist and their fractions are determined by the sample temperature and thermal history. The sample annealing leads to the growth of rigid fraction. It was found that below the glass transition temperature the only forms of large–scale mobility are the torsional vibrations and flips of para–phenylene groups, while spacer groups are virtually rigid. Above the glass temperature almost all phenylene rings undergo flipping motions and methylene groups of the spacer take part in complicated motions of both anisotropic and isotropic character.     

The effect of hydrogen bonding on the physical and mechanical properties of rigid‐rod polymers

The idea of competing effects between intramolecular and intermolecular hydrogen bonding was investigated. Results indicate that the formation of one type of hydrogen bond does not preclude the formation of the other. The strength of the intermolecular association was measured by ab initio calculations for several polymer systems, including methyl pendant poly(p‐phenylene benzobisimidazole) and poly‐{2,6‐diimidazo[4,5‐b:4′5′‐e]pyridinylene‐1,4(2,5‐dihydroxy)phenylene} (PIPD). Fibers with strong intermolecular association have high compressive strength and torsional modulus. The influence of intermolecular hydrogen bonding on torsional modulus is discussed in light of the transverse texture present in poly(p‐phenylene terephthalamide) and some other high‐performance fibers. Enhanced intermolecular interaction not only influences the aforementioned properties but also results in higher fiber density. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3053–3061, 2000     

Syntheses and Electronic Behaviors of Several Phenylene‐Chromium, ‐Molybdenum and/or ‐Tungsten Hybrid Copolymers

Four binary hybrid copolymers having chromium‐O‐phenylene, chromium‐S‐phenylene, molybdenum‐S‐phenylene, and tungsten‐S‐phenylene units, two ternary hybrid copolymers having molybdenum‐phenylene‐chromium and chromium‐phenylene‐tungsten units, and further, a quartic hybrid copolymer having a molybdenum‐phenylene‐chromium‐phenylene‐tungsten framework were synthesized, and their electronic behaviors were examined. The results of UV‐VIS, ESR, and XPS spectral analyses indicated that, in the ternary hybrid copolymers, an electron transfer takes place from chromium atom to either molybdenum or tungsten, and, in the quartic hybrid copolymer, an electron transfer takes place in the process of tungsten→molybdenum→chromium.     

The photophysical properties and morphology of fluorene-alt-benzene based conjugated polymer

A series of fluorene-alt-benzene based conjugated main chain polymers chemically attached with alkyl side chains of different lengths on phenylene rings were designed and synthesized by a palladium catalyzed Suzuki coupling reaction. The UV-vis absorption and fluorescence spectra, thermal stability of spectral property, phase transition behavior and morphology of the synthesized polymers were investigated. With increasing the length of the alkyl side chain, the UV and fluorescence spectra exhibit an obvious blue shift compared with those of the unsubstituted polymer. The alkyl substitution improves the thermal spectral stability of the polymers due to the steric hindrance of the alkyl side chains, thus leading to efficient separation of the main chain backbones. The phase transition behavior is closely related to the length of the alkyl side chains attached on the phenylene rings. The annealed films of the polymers display characteristic nematic liquid crystalline texture. TEM observations indicate that solvent-cast thin deposits of all the polymers show typical fibrillar morphology.     

Modeling the effects of torsional disorder on the spectra of poly- and oligo-(p-phenyleneethynylenes)

The absorption spectra of phenyleneethynylene oligomers show an unusual change in shape with oligomer length. The unusual aspects of the spectra arise from rotation of the phenylene rings about the long axis of the oligomer. In the ground electronic state, the barrier to this rotation is low and the spectra in room temperature come from an ensemble of different structures. In the excited electronic state, the barrier to rotation is substantially higher, giving rise to strong nonlinear electron-phonon coupling. A multidimensional semiempirical model that includes these effects is developed for the photophysics of phenyleneethynylene oligomers. The ground-state energy is modeled with a molecular mechanics expression, and the excitation energy is modeled with an exciton model. Intermediate Neglect of Differential Overlap/Singles Configuration Interaction (INDO/SCI) calculations verify the exciton model and provide initial estimates of the model parameters. These parameters generate the qualitative features seen in experimental spectra. Inclusion of entropy effects from the multiple torsional coordinates is essential. Refinement of the parameters yields quantitative agreement with experiment. This agreement shows that coupling to torsional motion is a major factor in the spectroscopy and photophysics of these conjugated polymers.     

Conformationally tuned large two-photon absorption cross sections in simple molecular chromophores

We investigate here the relationship between molecular architecture and two-photon absorption (TPA) processes in a class of alkyl-substituted 4-quinopyran chromophores. We find that TPA cross sections diverge as the one-photon gap energy nears one-half of the two-photon gap. The molecular strategy proposed here to tune these two-excitation gaps for maximizing TPA cross sections is to twist the molecule about the bond connecting the chromophore donor and acceptor phenylene fragments. Extremely large TPA cross sections, determined by the absorption bandwidth, can then be realized (imaginary part of the third-order polarizability approximately 2.6 x 10(5) x 10(-36) esu) for fundamental photon energies near 1.0 eV, when the torsional angle approaches 104 degrees. The required torsional angle is achieved by introduction of sterically encumbered 2,2',2' ',2' " tertiary alkyl substituents.     

FLUORENE-BASED LIGHT-EMITTING POLYMERS

Several series of fluorene-based light-emitting polymers with the emphasis on achieving efficient and stable bluelight emission are reported. Spiro-functionalization may narrow the emission spectra (with smaller tail at Ionger wavelengths)of fluorene homopolymers to provide purer blue emission. The thermal spectral stability of the polymers could also beimproved because of the elevation of the glass transition temperature caused by the spiro-functionalization. However, theexcimer emission in fluorene homopolymers is not suppressed by the spiro-functionalization. Alternate copolymers of 9,9-dihexylfluorene and substituted phenylenes may emit efficient blue ligh both in solution and in film. The optical propertiesare dependent on the substituion on the phenylene ring. The alkoxy-substituted polymers displayed efficient PL and EL andgood thermal spectral stability. The HOMO and LUMO energy levels of the polymers based on the backbone structure couldbe tuned in a wide range by attaching different functional groups on the phenylene ring. By attaching europium(III) complexat the ends of the side chains in the alternate copolymers, we have demonstrated a new approach to achieving red emissionwith a very narrow spectrum. The copolymers of 9,9-dihexylfluorene and thiophene and bithiophene with differentsubstitutions were also synthesized to study the effect of substitution and regioregularity on the optical and other physicalproperties of the polymers.     

First principle studies of charge transport in PPV polymer under conformational deformation

We consider the inclusion of torsional deformations in the structure of an infinite chain of poly‐p‐phenylene vinylene and study the consequences on charge transport along the polymer length. Calculations of the electronic transport are performed with density functional theory combined with Keldysh nonequilibrium Green's function method. Deformations are modeled either as a sharp rotation of the polymer backbone about a single chemical bond or as a continuous twist extending along various monomer units. We study current‐voltage (I‐V) characteristics in a two probe configuration as a function of angle and degree of torsional sharpness and demonstrate that when the backbone torsion is abrupt a barrier to electron transport builds up that becomes maximum at an angle of 100°. The outcome of our calculations is that the abrupt twist of the polymer backbone creates two virtually disconnected segments, which validates models that treat a real polymer as distribution of chains of different sizes and conjugation lengths. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 578–586     

Intramolecular electronic excitation energy transfer in donor/acceptor dyads studied by time and frequency resolved single molecule spectroscopy

Electronic excitation energy transfer has been studied by single molecule spectroscopy in donor/acceptor dyads composed of a perylenediimide donor and a terrylenediimide acceptor linked by oligo(phenylene) bridges of two different lengths. For the shorter bridge (three phenylene units) energy is transferred almost quantitatively from the donor to the acceptor, while for the longer bridge (seven phenylene units) energy transfer is less efficient as indicated by the occurrence of donor and acceptor emission. To determine energy transfer rates and efficiencies at the single molecule level, several methods have been employed. These comprise time-correlated single photon counting techniques at room temperature and optical linewidth measurements at low temperature (1.4 K). For both types of measurement we obtain broad distributions of the rate constants of energy transfer. These distributions are simulated in the framework of Forster theory by properly taking into account static disorder and the flexibility of the dyads, as both effects can substantially contribute to the distributions of energy transfer times. The rate constants of energy transfer obtained from the calculated distributions are smaller on average than those extracted from the experimental distributions, whereby the discrepancy is larger for the shorter bridge. Furthermore, by plotting the experimentally determined transfer rates against the individual spectral overlaps, approximately linear dependencies are found being indicative of a Forster-type contribution to the energy transfer. For a given single molecule such a linear dependence could be followed by spectral diffusion induced fluctuations of the spectral overlap. The discrepancies between measured energy transfer rates and rates calculated by Forster theory are briefly discussed in light of recent results of quantum chemical calculations, which indicate that a bridge-mediated contribution is mainly responsible for the deviations from Forster theory. The availability of the inhomogeneous distributions of donor and acceptor electronic transition frequencies allows for comparing the energy transfer process at liquid helium and room temperature for the same set of molecules via simple simulations. It is found that on average the energy transfer is by a factor of approximately 3 faster at room temperature, which is due to an increase of spectral overlap.     

Conformational analysis of highly extended poly(ethylene terephthalate) chains by Monte Carlo calculations

The conformational disorder compatible with the highly extended chains found in mesomorphic poly(ethylene terephthalate) has been studied by Monte Carlo calculations on model oligomers confined inside cylindrical tubes. The distribution of torsional angles for such extended chains is characterized by O C C O bonds being always in the trans domain, while the C O C C bonds show an approximately similar probability of being found in trans and gauche states, the probability maxima being centered at 90° and −90° in the latter cases. At variance with the torsional angles of the O C C O and the ester bonds, always very close to 180°, the distributions for all other torsional angles show flat and broad probability maxima, indicating the possibility of substantial deviations from the average value inside each domain. This is also true for the fictitious O C˙˙˙C O bonds across the phenylene rings, for which a nearly trans geometry is preferred in extended conformations.     

Low-temperature mechanical relaxations in polymers containing aromatic groups

Studies have been made of the secondary relaxation processes in the solid state of a number of polymers containing aromatic groups in the polymer chain. The polymers investigated include one, polystyrene, with the aromatic group in side-chain positions, and six high polymers in which phenylene rings lie in the main backbone chain. In polystyrene, wagging and torsional motions of the side chain phenyl rings give rise to a low-temperature δ-relaxation which is centered at 33°K (1.7 Hz) and which has an activation energy of about 2.3 kcal/mol. Most of the polymers with phenylene rings in the main chain exhibit a low-temperature relaxation in the temperature region from 100°–200°K. This relaxation process is centered at 159°K (0.54 Hz) in poly-p-xylylene, at 162°K (0.67 Hz) in polysulfone, and at 165°K (1.24 Hz) in poly(diancarbonate). In poly(2,6-dimethyl-p-phenylene oxide), two overlapping low-temperature relaxations are found, one in the range 125–140°K and the other near 277°K (ca. 1 Hz). The low-temperature secondary relaxation process in all of these polymers is believed to be associated with local reorientational motion of the phenylene, or substituted phenylene, rings or with combined motion of the phenylene rings and nearby chain units. For these low temperature relaxation processes, the activation energy is about 10 kcal/-mole. The temperature location of the relaxation appears to depend on the specific units to which the phenylene rings are attached and on steric and polar effects caused by substituents on the ring. In the poly-p-xylylenes the relaxation is shifted to much higher temperatures by a single Cl substitution on the ring but remains at essentially the same temperature position when dichlorosubstitution is made. The effects of water on the magnitude and temperature location of the observed low temperature relaxations, as well as the implications of the study for other polymers containing aromatic groups in their backbone chains, are discussed.     

O-H stretch overtone excitation of ethyl hydroperoxide conformers

We present laser photoacoustic spectra of ethyl hydroperoxide (EHP) for 3-6 quanta of O-H stretch. Spectra are consistent with ab initio spectral simulations that take into account the influence of torsional motion about the O-O bond on O-H stretch overtone excitation. Experimental and simulated spectra share two trends. First, spectral features due to torsional excitation, including hot bands, become more prominent with increasing O-H stretch excitation, as has been shown previously for similar molecules such as methyl hydroperoxide. Second, contributions from the two different EHP conformers become clearly distinguishable at higher O-H stretch excitation, mainly due to the role of torsional motion. Results are consistent with a higher energy separation (330 cm(-1)) between the lower energy anti and the higher energy gauche conformers than predicted by electronic structure calculations (137 cm(-1)). Calculated absorption intensities are consistently higher than experimental values by ~30% but within the experimental uncertainty. With each additional O-H stretch overtone, the dropoff in calculated integrated absorption intensities at room temperature becomes less extreme, with a 14-fold dropoff from 3ν(OH) to 4ν(OH) and an 8-fold decrease from 5ν(OH) to 6ν(OH).     

Guests Like Gear Levers: Donor Binding to Coordinatively Unsaturated Metal Sites in MIL-101 Controls the Linker′s Rotation

We present investigation of the effect of electron-donor guests on framework mobility in the metal–organic framework (MOF) MIL-101(Cr) monitored by solid state ²H NMR spectroscopy. In a guest-free material, the mobile phenylene fragments of the terephthalate (TP) linkers populate two fractions with notably different kinetic parameters for torsional motion. Two fractions of rotational motion are indicative of non-equivalence of TP linker binding to the Cr₃O trimer, the primary building unit of the MIL-101 framework. It is established that the interaction of the guest molecules with coordinatively unsaturated metal sites (CUS) of the MOF dramatically decreases torsional barriers for the linker motions, enhancing the rotation rate. This result is opposite to a more conventional slowing down effect on the linker rotation of the guests not selectively interacting with the adsorption sites inside the framework of the MOFs. The effect of coordination on both the torsional barrier and the rotation rate depends notably on the particular guest interacting with the CUS. The found effects of the guest on the rotational motion represent a basis for developing the strategy for ruling and controlling the linker rotation in MOFs with CUS. It is shown that if water occupies CUS, another guest (tert-butanol, cyclohexanone) fails to competitively coordinate to the site.     

Beiträge zur Chemie der Pyrrolpigmente, 24. Mitt. Über die Beziehung zwischen Lichtabsorption und Struktur von Bilatrienen-abc

Using the recently established solution structure of a bilatriene-abc derivative the parameter set of thePPP-SCF-LCAO-MO-Cl model was refined. The general trend, that molecular configuration itself does not so much determine the absorption spectra as was deduced by investigation of partial bile pigment structures, was confirmed for the bilatrienes-abc. Instead, the configuration at a particular double bond induces a certain torsional angle at the adjacent single bond which leads to dramatic spectral changes on isomerization of this double bond. Isomerization without this torsional effect brings about different relative intensities of the two main spectral bands. Comparing measured spectra of several bilatrienes-abc and calculated spectra a helicalsyn, syn, syn-conformation with three torsional angles at the methine fragments of appr. 20° was deduced for systems with (Z, Z, Z)-configuration. For a recently prepared (E, Z, Z)-derivative a nearly helicalsyn, syn, syn-conformation with torsional angles of 40°, 20° and 20° at the methine single bonds is the most probable.

---

---

23. Mitt.:H. Falk, K. Grubmayr undK. Thirring, Z. Naturforsch.33b, 924 (1978).     

Toward a four-toothed molecular bevel gear with C2-symmetrical rotors

The design, synthesis, conformational analysis, and variable-temperature NMR studies of pentiptycene-based molecular gears Pp(2)X, where Pp is the unlabeled (in 1H) or methoxy groups-labeled (in 1OM) pentiptycene rotor and X is the phenylene stator containing ortho-bridged ethynylene axles, are reported. The approach of using shape-persistent rotors of four teeth but C(2) symmetry for constructing four-toothed molecular gears is unprecedented. In addition, the first example of enantioresolution of chiral pentiptycene scaffolds is demonstrated. Density functional theory (DFT) and AM1 calculations on these Pp(2)X systems suggest two possible correlated torsional motions, geared rocking and four-toothed geared rotations, which compete with the uncorrelated gear slippage. The DFT-derived torsional barriers in 1H for rocking, four-toothed rotation, and gear slippage are approximately 2.9, 5.5, and 4.7 kcal mol(-1), respectively. The low energy barriers for these torsional motions result from the low energy cost of bending the ethynylene axles. Comparison of the NMR spectra of 1OM in a mixture of stereoisomers (1OM-mix) and in an enantiopure form (1OM-op) confirms a fast gear slippage in these Pp(2)X systems. The effect of the methoxy labels on rotational potential energy surface and inter-rotor dynamics is also discussed.     

Molecular mechanics analysis of polymer conformation, 4. Local chain motions and molecular relaxations of poly(parabanic acids)

The structure of the repeating units of poly(parabanic acid) (PPA), a polyimide-like glassy heat resistant polymer, was analyzed by MM2 using various model compounds of PPA-M and PPA-T consisting of M (1,3-diazolidine-2,4,5-trione-1,3-diyl-1,4-phenylenemethylene-1,4-phenylene) and T (1,3-diazolidine-2,4,5-trione-1,3-diyl-3,3′-dimethyl-4,4′-biphenylylene) units, respectively. Based on the most stable structures obtained, the subunit rotations of the methylene, phenylene, and diazolidine groups were evaluated. The potential mobilities estimated for these subunits can reasonably be correlated with the dynamic mechanical and dielectric properties of PPA. The γ relaxation mode of both PPA-M and a copolymer PPA-TM is reasonably explained by the rotation of the methylene group. The major mode of the β relaxations of both PPAs is ascribed to the rotation of the phenylene ring of the M unit, while the β^* dielectric relaxation is attributed to the torsional vibration of the parabanic ring involving the adjacent aromatic moieties. These data suggest that PPA is similar to polycarbonate rather than polyimide in terms of the local chain motion. It is shown that the conformational analysis by MM2 is quite informative to understand the structure property relationships of polymers.     

Thermal degradation of polymers with phenylene units in the chain. I. Polyphenylenes and poly(phenylene oxides)

The thermal degradation of polyphenylenes and poly(phenylene oxides) was studied under vacuum at temperatures between 350 and 620°C. The volatile and solid degradation products were analyzed by mass spectroscopy, infrared spectroscopy, and elemental analysis. Overall mechanisms for the thermal breakdown have been proposed. Polyphenylene decomposes to form polymer carbon, while hydrogen is the major volatile product. Some ring breakdown occurs with evolution of methane. Poly(phenylene oxide) forms mainly low molecular weight chain fragments, partially with hydroxyl endgroups. Some of the ether linkages decompose with ring breakdown, yielding carbon monoxide, water, and some carbon dioxide. Pendent groups on polyphenylenes and poly(phenylene oxides) are removed at the lower temperatures. The hydroxyl group yields essentially carbon monoxide and dioxide (the carbon being supplied by the rings), the methyl group methane, and the methoxy group methane and some methanol.     

Free-jet studies of the visible spectroscopy of some perhalonitrosomethanes

Recent work on the electronic spectroscopy of halogen substituted nitrosomethanes in the visible spectral region is reviewed with particular reference to laser-induced fluorescence and photofragment yield spectra in supersonic free-jet expansions. The A(n, π*)-X electronic spectra in the 650–720 nm region are dominated by progressions in low frequency torsional modes, that reflect eclipsed to staggered dihedral conformational changes upon electronic excitation. The observed torsional progressions can be understood well on the basis of spectral simulations that utilize a simple one-dimensional Hamiltonian for the hindered internal rotation. The relevance of these laser spectroscopic studies for current work on the state-selected photophysics and photodissociation dynamics of the title compounds is highlighted.     

Ab initio torsional potential and transition frequencies of acetaldehyde

High-level ab initio electronic structure calculations, including extrapolations to the complete basis set limit as well as relativistic and diagonal Born-Oppenheimer corrections, resulted in a torsional potential of acetaldehyde in its electronic ground state. This benchmark-quality potential fully reflects the symmetry and internal rotation dynamics of this molecule in the energy range probed by spectroscopic experiments in the infrared and microwave regions. The torsional transition frequencies calculated from this potential and the ab initio torsional inverse effective mass function are within 2 cm(-1) of the available experimental values. Furthermore, the computed contortional parameter rho of the rho-axis system Hamiltonian is also in excellent agreement with that obtained from spectral analyses of acetaldehyde.