Polarized luminescence from self-assembled, aligned, and cleaved supramolecules of highly ordered rodlike polymers (original) (raw)

Self-assembled, aligned, and cleaved supramolecules of poly (2, 5-pyridinediyl)

2002

We report on directed self-assembly in supramolecules containing rod-like polymers. The comb-shaped supramolecules consist of poly(2,5-pyridinediyl), camphorsulfonic acid, and hydrogen bonded amphiphilic side chains. Locally they form highly ordered lamellar structures in which the polymers are stacked. The liquid crystalline state allows facile overall alignment yielding absorption dichroism and polarized photoluminescence. After alignment, cleavage of the amphiphiles results in solid films which retain this optical anisotropy with the high photoluminescence quantum yield. P11.5.1 Mat. Res. Soc. Symp. Proc. Vol. 725 © 2002 Materials Research Society P11.5.5

Functional Materials Based on Self-Assembly of Polymeric Supramolecules

Science, 2002

Self-assembly of polymeric supramolecules is a powerful tool for producing functional materials that combine several properties and may respond to external conditions. We illustrate the concept using a comb-shaped architecture. Examples include the hexagonal self-organization of conjugated conducting polymers and the polarized luminance in solid-state films of rodlike polymers obtained by removing the hydrogen-bonded side chains from the aligned thermotropic smectic phase. Hierarchically structured materials obtained by applying different self-organization and recognition principles and directed assembly form a basis for tunable nanoporous materials, smart membranes, preparation of nano-objects, and anisotropic properties, such as proton conductivity.

Diffraction analysis of highly ordered smectic supramolecules of conjugated rodlike polymers

Journal of Applied Crystallography, 2003

A small/wide-angle X-ray scattering and grazing incidence diffraction study of comb-shaped supramolecules of conjugated poly(2,5-pyridinediyl), acid dopant and hydrogen bonded amphiphilic side chains is reported. In solution, polymers are dissolved rodlike particles. When the side-chains are introduced, polymers self-assemble in hierarchic liquid crystals (LC). Diffraction patterns of aligned LC show h00, 020, and 004 reflections, and additional small-angle reflections along the polymer axis. A triangular correlation function indicating a very large correlation length is seen along the smectic axis. An aligned solid structure can be formed by cleaving side chains from the aligned LC.

Supramolecular assembly of conjugated polymers: From molecular engineering to solid-state properties

Materials Science and Engineering: R: Reports, 2006

Conjugated polymers are important materials with unique electrical and optoelectronic properties, and have found applications in a variety of molecular electronic devices including light-emitting diodes, solar cells, field effect transistors, photodetectors, sensors, and nonlinear optics. [1] Polyoxometalates (POMs), a large group of metal oxide clusters consisting of early-transition-metal cations and oxo ligands, are also considered electrically active materials and have attracted increasing interest in recent years due to their outstanding properties in catalysis, medicine, and photoelectronic responses. Incorporating POM clusters covalently with conjugated polymers may lead to hybrid materials with not only value-adding properties, but also synergistic effects. For example, POM-containing hybrid polymers have been found to be good candidates for photovoltaic cells, photocatalytic materials, and catalytic nanoparticles. While it is known that the device performance of hybrid materials depends strongly on their aggregated micro-or nanostructures, there has been very little research on the aggregation of POM-containing conjugated polymers in both solution and solid states. Such studies are essential if POM-based controllable ordered structures are to be realized.

Photoluminescence Spectra of Self-Assembling Helical Supramolecular Assemblies: A Theoretical Study

The Journal of Physical Chemistry B, 2008

The reversible assembly of helical supramolecular polymers of chiral molecular building blocks is known to be governed by the interplay between mass action and the competition between weakly and strongly bound states of these building blocks. The highly co-operative transition from free monomers at high temperatures to long helical aggregates at low temperatures can be monitored by photoluminescence spectroscopy that probes the energetically lowest-lying optical excitations in the assemblies. In order to provide the interpretation of obtained spectroscopic data with a firm theoretical basis, we present a comprehensive model that combines a statistical theory of the equilibrium polymerization with a quantum-mechanical theory that not only accounts for the conformational properties of the assemblies but also describes the impact of correlated energetic disorder stemming from deformations within the chromophores and their interaction with solvent molecules. The theoretical predictions are compared to fluorescence spectra of chiral oligo(p-phenylene-vinylene) molecules in the solvent dodecane and we find them to qualitatively describe the red-shift of the main fluorescence peak and its decreasing intensity upon aggregation.

Formation and properties of liquid crystalline supramolecules with anisotropic fluorescence emission

Polymer Chemistry, 2014

Two kinds of liquid crystalline (LC) supramolecules with anisotropic fluorescence emission were prepared by ionic self-assembly from a copolymer, derived from acrylic acid and 6-(4 0 -cyanobiphenyl-4-yloxy)hexyl acrylate, and oppositely charged fluorescent molecules: stilbene-based rod-like dye (Stil) or tetraphenylethene-based propeller-like dye (TPE). The supramolecules exhibited a nematic LC nature and the different structure of the fluorescent units showed different effect on the LC behaviour of the supramolecules. After being spin-coated onto an oriented PVA film, the liquid crystalline supramolecule film was thermally annealed and the anisotropic fluorescence emission was investigated. A different thermal amplification effect was found depending on the different structure of the fluorescent unit. This conclusion provides a new perspective on the design of a high-performance fluorescence polarization film. † Electronic supplementary information (ESI) available: The synthesis of TPE6N and CP91-TPE6N, Fig. S1-S6. See

Host–Guest Driven Self‐Assembly of Linear and Star Supramolecular Polymers

2008

MHz) spectrometer. All chemical shifts (δ) were reported in ppm relative to the proton resonances resulting from incomplete deuteration of the NMR solvents. 31 P NMR spectra were obtained using a Bruker AMX-400 (162 MHz) spectrometer. All chemical shifts (δ) were recorded in ppm relative to external 85% H 3 PO 4 at 0.00 ppm. Electrospray ionization ESI-MS experiments were performed on a ArH); 4.39 (t, 4H, ArCH, J = 7.7 Hz); 3.58 (t, 2H, CH 2 CH 2 OH, J = 6.3 Hz); 2.36-2.23 (m, 8H, ArCHCH 2); 2.04 (s, 12 H, ArCH 3); 1.49 (m, 2H, CH 2 CH 2 CH 2 OH); 1.28 (m, 6H, CH 2 CH 2 CH 3); 0.93 (t, 9H, CH 2 CH 2 CH 3 , J = 7.3 Hz). ESI-MS: m/z calcd for C 44 H 56 O 9 (729.4 Da) [M-H]-: 728.4; found 728.

Self-Organization of Nitrogen-Containing Polymeric Supramolecules in Thin Films

MRS Proceedings, 2000

Rigid rod-like poly(2,5-pyridinediyl), semi-rigid polyaniline and flexible poly(4vinylpyridine) are nitrogen-containing polymers that with selected amphiphilic oligomers form self-organized comb-shaped supramolecules due to protonation, hydrogen bonding and polarnonpolar effects combined. Luminescent or conductive ordered structures are demonstrated in thin films. The structures are characterized using small-angle x-ray scattering (SAXS) and grazing-incidence small-angle x-ray scattering (GISAXS). The uniformity is studied using atomic force microscopy and scanning near-field optical microscopy (SNOM).