Synthesis and spectral investigation of alkyl methacrylates with halogenated carbazolyl pendant groups for photonics applications

The alkyl methacrylates with halogenated carbazolyl pendant groups were prepared, and the analysis of their absorption and emission spectra showed that the polymers containing monohalogenatged carbazole rings were capable of exhibiting a high singlet‐triplet (S‐T) conversion. The reasons that mainly triplet excitons could be observed in such polymers and additional bands appearance in the spectra of the polymers with dihalogenated carbazole rings are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1650–1656, 2002; DOI 10.1002/app.10469     

Charge-carrier relaxation dynamics of poly(3-hexylthiophene)-coated gold hybrid nanoparticles

Poly(3-hexylthiophene)-coated gold (Au@P3HT) hybrid nanoparticles have been prepared via a “grafting-to” approach, and compared with pristine P3HT to investigate the dynamics of exciton relaxation using time-resolved transient-absorption and fluorescence spectroscopy. In efforts to facilitate the efficient dissociation of photo-generated excitons, we have incorporated gold nanoparticles having surface-plasmon resonances into thiol-terminated P3HT to fabricate Au@P3HT nanocomposites. The first-excited singlet state of Au@P3HT decays faster than that of pristine P3HT due to interactions with surface-plasmon resonances; excitons undergo dissociation via energy transfer from P3HT to the surface-plasmon state of a gold nanoparticle in Au@P3HT nanocomposites. The lowest triplet state of P3HT is also less populated due to the energy transfer while its lifetime is slightly reduced by the presence of gold nanoparticles. Thus, it is suggested that our incorporation of gold nanoparticles into P3HT reduces the recombination of geminate excitons and, thereby, increases the probability of exciton dissociation.     

Synthesis of oxadiazole‐based polymers containing a carbazole–vinylene or fluorene–vinylene group and their hole‐injection/transport behavior in light‐emitting diodes

A series of conjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenyl)‐1,3,4‐oxadiazole]}) and nonconjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) and poly{9,9‐dihexyl‐2,7‐fluorene–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) polymers containing oxadiazole and carbazole or fluorene moieties in the polymer backbone were synthesized with a multiple‐step procedure. The properties of the polymers, including the photophysical and electrochemical characteristics, could be fine‐tuned by adjustment of the components or structures in the polymer chains. The polymers were used to examine the hole‐injection/transport behavior as hole‐injection/hole‐transport layers in double‐layer indium tin oxide (ITO)/polymer/aluminum tris(8‐hydroxyquinoline)/LiF/Al devices by the determination of their energy levels. The effects of the polymers in these devices on the charge‐transport behavior were compared with a control device fabricated with poly(ethylenedioxythiophene) (PEDOT)–poly(styrene sulfonate) (PSS). Devices containing the synthesized polymers showed comparable adhesion to the ITO anode and good hole‐injection/transport performance. In addition, they exhibited higher electroluminescence over an identical range of current densities than the control device. This was attributed to the prevention of radiative exciton quenching caused by the PEDOT–PSS interfaces and the improvement of electron/exciton blocking due to the higher electron affinity of the synthesized polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Recent Advances in Luminescent Transition Metal Polyyne Polymers

This review briefly summarizes research work carried out by the author in the past decade on rigid-rod transition metal polyyne polymers and their molecular precursors. The research involves the synthesis, spectroscopic and photophysical characterization, ligand functionalization, and possible optoelectronic applications of transition metal polyyne polymers. Herein, oligomeric and polymeric metal alkynyl systems of the late transition metals are discussed, and particular attention is focused on the electronic absorption spectroscopy and photoluminescence behavior, thermal stability and structural aspects of these polymetallaynes. A detailed account of the evolution of the first excited singlet and triplet state on the electronic structure of the organic spacer groups of these metal polyyne polymers is also given and the interplaying factors that govern the spatial extent of the lowest-lying singlet and triplet energy levels for the chemical tailoring of the singlet–triplet gap are elucidated. The possible developments of this research are also envisaged.     

Theoretical investigation on the ground- and excited-state properties of novel octupolar oligothiophene-functionalized truxenes and dipolar analogs

The density functional theory (DFT) is used to compute the ground-state geometries, ionization potentials (IPs), electron affinities (EAs) and HOMO-LUMO gaps (ΔE_H-L) of novel octupolar oligothiophene-functionalized truxenes and the corresponding dipolar analogs. The lowest singlet excited-state geometries of some oligomers have been investigated by the singles configuration interaction (CIS) method. The absorption and emission spectra are calculated by time-dependent DFT (TDDFT) on the basis of the ground- and excited-state geometries, respectively. Our calculations are in good agreement with the available experimental results. The calculated results show that all oligomers are nonplanar in their ground electronic states. The structural relaxation upon excitation results in the planarity of dipolar oligomers and one branch of octupolar oligomers. Because fluorene and truxene segments in two series are not the repeated units of oligomers, the chain dependence of IPs, EAs, ΔE_H-L and excitation energies do not follow the usual linear 1/n rule. We have used three plotted points closest to polymer to plot lines; and extrapolated the resultant linear relationship to infinite chain length; and finally obtained the relative properties of polymers.     

Magnetic field dependence of singlet oxygen generation by nanoporous silicon

Energy transfer from photoexcited excitons localized in silicon nanoparticles to adsorbed oxygen molecules excites them to the reactive singlet spin state. This process has been studied experimentally as a function of nanoparticle size and applied external magnetic field as a test of the accepted understanding of this process in terms of the exchange coupling between the nano-Si exciton and the adsorbed O₂ molecules.     

Pd‐complex‐catalyzed synthesis of oligomers having a recurring benzodiazaborole unit in the main chain

BACKGROUND: Rigid‐rod oligomers and polymers comprising a recurring benzodiazaborole unit show high thermal stability and intriguing optical and electrochemical properties due to the expanded electron system through the B? C and B? N bonds in the main chain by the use of the p_z orbital on boron. However, the conventional method for the preparation of these oligomers and polymers often requires polycondensation under severe conditions. In this study, we report the synthesis of oligomers comprising a recurring benzodiazaborole unit using the Stille reaction under mild conditions. In addition, we describe their chemical properties and solid‐state structures. RESULTS: The reaction of 3,3′‐diaminobenzidine with 4‐bromophenylboronic acid and benzeneboronic acid yielded 2,2′‐bis(4‐bromophenyl)‐2,3,2′,3′‐tetrahydro‐1H,1′H‐[5,5′]bi(benzo[1,3,2]diazaborolyl) (1) and 2,2′‐biphenyl‐2,3,2′,3′‐tetrahydro‐1H,1′H‐[5,5′]bi(benzo[1,3,2]diazaborolyl), respectively. Pd‐complex‐catalyzed polycondensation of 1 with bis(tributyltin) and bis(tributylstannyl)acetylene in N,N‐dimethylformamide provided oligomers comprising a recurring benzodiazaborole unit in 98 and 97% yields, respectively. CONCLUSION: The oligomers comprising a recurring benzodiazaborole unit were obtained under mild reaction conditions in high yields. The expansion of the electron system through the B? C and B? N bonds of the oligomers was confirmed by UV‐visible spectroscopy. The oligomers were photoluminescent in solution and electrochemically active in a film, and they assumed self‐assembled stacked structures in the solid state. Copyright © 2008 Society of Chemical Industry     

Interface‐tailored and nanoengineered polymeric materials for (opto)electronic devices

For plastic (opto)electronic devices such as light‐emitting diodes (LEDs), photovoltaic (PV) cells and field‐effect transistors (FETs), the processes of charge (hole/electron) injection, charge transport, charge recombination (exciton formation), charge separation (exciton diffusion and dissociation) and charge collection are critical to enhance their performance. Most of these processes are relevant to nanoscale and interfacial phenomena. In this review, we highlight the state‐of‐the‐art developments of interface‐tailored and nanoengineered polymeric materials to optimize the performance of (opto)electronic devices. These include (1) interfacial engineering of anode and cathode for polymer LEDs; (2) nanoengineered (C₆₀ and inorganic semiconductor nanoparticles) π‐conjugated polymeric materials for PV cells; and (3) polymer and monolayer dielectrics/interfaces for FETs and light‐emitting and nano‐FETs. Copyright © 2009 Society of Chemical Industry     

Synthesis and properties of oxetane monomers and oligomers with electro‐active pendent groups

BACKGROUND: Monomers and polymers carrying pendent electro‐active fragments are widely studied due to their application in various optoelectronic devices. Monomers containing triphenylamino, triphenyldiamino and carbazol‐9‐yl fragments with vinyl, epoxy or acryl functional groups are mostly used. The synthesized materials are used for preparation of hole transport layers as well as host materials for electrophosphorescent light‐emitting diodes. Much fewer presentations are reported on the preparation of monomers containing other electro‐active or functional groups. RESULTS: Here we describe oxetane monomers and their oligomers containing various electro‐active pendent groups. The weight‐average molecular weights of the oligomers are in the range 1420–3250 g mol^?1 with a molecular weight distribution of 1.7–4.1. The electron photoemission spectra of amorphous layers of the compounds established ionization potentials of 5.55–5.85 eV. Room temperature hole drift mobility in the layers of some oligomers exceeds 10^?7 cm² V^?1 s^?1 at high electric fields. CONCLUSION: The synthesized oligomers exhibit promising thermal and film‐forming properties. Amorphous layers of some of the materials demonstrate suitable ionization potentials and sufficient hole transport properties for their application in optoelectronic devices. Copyright © 2008 Society of Chemical Industry     

Synthesis and characterization of red light-emitting electrophosphorescent polymers with different triplet energy main chain

Red light-emitting electrophosphorescent polymers with poly(fluorene-alt-carbazole) (PFCz) and poly(3,6-carbazole) (PCz) as the main chain, and the quinoline-based iridium (Ir) complex as the side chain have been synthesized by Suzuki and modified Yamamoto polymerization, respectively. The triplet energy of the polymeric backbone is tuned from 2.1 eV of polyfluorene (PF) to 2.3 eV of PFCz and 2.6 eV of PCz. We find that, with the increasing triplet energy, the lifetime of the triplet excitons gradually increases, but the device efficiency becomes worse. The reason is that the alteration of the main chain structure leads to the increase of the highest occupied molecular orbital (HOMO) level of the polymeric host, which can facilitate the efficient hole injection and transportation. As a consequence of this enhancement of the hole current, charge balance in the emitting layer is destroyed, and correspondingly, the poorer device performance is achieved. Our results, we believe, indicate that besides the triplet energy, charge balance is a crucial determinant to develop high efficiency red light-emitting electrophosphorescent polymers.     

热活性型延迟荧光材料的研究进展

有机电致发光二极管（OLED）在全彩色平板显示和固态照明领域具有广泛的应用而倍受关注。在电场激发下,单重态激子与三重态激子的比值为1∶3。传统的荧光材料只能利用单重态激子发光,内部量子效率（IQE）最高为25%。热活性型延迟荧光（TADF）材料可将三重态激子反系间跨越（RISC）到单重态能级而发出延迟荧光,理论上内部量子效率可达100%。设计TADF材料的关键在于分子要同时满足高荧光量子产率和小的第一激发单重态与第一激发三重态能级差（ΔE_ST）。综述了近几年TADF材料的研究进展,重点介绍了TADF材料的设计思想和器件性能。     

Electroluminescence in Semiconducting Conjugated Polymers and Oligomers: A Quantum-chemical Perspective

Abstract

We discuss in this contribution the ability of quantum-chemical calculations to describe the essential aspects of one of the most promising applications of semiconducting conjugated polymers and oligomers, i.e., their use as active layers in light-emitting diodes (LEDs). We present an overview of the results of recent theoretical studies that we have performed on oligomers representative of polyparaphenylenevinylene and polythio-phene. We mostly deal with: (i) the modelling of the linear optical properties of the conjugated polymers involved in the emitting layer, taking into account the vibronic structure; (ii) the investigation of the relative locations of. and relaxation phenomena taking place in. the lowest singlet and triplet excited states; and (iii) a general discussion of the various terms contributing to the polaron-exciton binding energy.     

Optical and electrochemical properties of oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s with self‐assembled ordered structures in solid state

Oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s were synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene)‐promoted condensation reactions of 1,5‐dialkoxy‐2,6‐dibromonaphthalenes. The UV–Vis, photoluminescence (PL), and powder X‐ray diffraction (XRD) measurements suggested that the oligomers have a self‐assembling ordered structure in the solid state. The oligomers underwent electrochemical oxidation (p‐doping), which occurred at lower potentials for films than for acetonitrile solutions containing [Et₄N]BF₄. This effect is caused by the longer π‐conjugation lengths of the oligomers in films, which was attributed to molecular self‐assembly leading to ordered structures in the solid state. The electrochemical reaction of the oligomers was accompanied by electrochromism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41840.     

Polymer LEDs as a physics tool

We present a systematic experimental and theoretical study of physical mechanisms governing the operation of polymer light-emitting diodes. We show that through self-consistent modeling we can address both charge transport and exciton generation. Electron and hole mobility in several polymers has been characterized experimentally. Characterization of excitons and especially of triplet-excitons is achieved through use of a triplet-emitting molecule.     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Photophysical processes in poly(hexamethylene adipamide)–acid dye complexes: Energetics of nylon 66 phototendering

The mechanism of dye-sensitized photo-oxidative degradation of nylon 66 was investigated. A known phototendering dye, C.I. Acid Blue 40 (1-amino-4-(p-aminoacetanilide)-2-anthraquinone sodium sulfonate), was used for this study. Excitation and emission spectra of the dyed and undyed nylons indicated that a ground-state complex between the dye and the polyamide was formed upon dyeing. The energy level of the complex's electronic states favor triplet–triplet energy transfer from the nylon to the complex. Quenching studies show that the energy transfer occurs efficiently with a rate constant of 45.8 l. mole^?1 sec^?1. An additional energy transfer occurs between the excited free dye and the complex by either a singlet–triplet or a triplet–triplet mechanism. Kinetic analysis of the nylon-complex energy transfer suggests that the triplet energy of nylon migrates 24 to 33 Å along the amide chromophores in an exciton fashion until an energy trapping complex is reached. Energy is then transferred by an exchange mechanism. Photo-oxidative studies verify that the dye–nylon complex sensitizes the polyamide photo-oxidative degradation at its own expense without dye photobleaching.     

DC electrical conductivity of some oligoazomethines

Six aromatic oligoazomethines were synthesized containing seven benzene rings each. The terminal rings were substituted with different groups, namely, H, Cl, NO₂, OH, OCH₃ and CH₃. The synthesis was carried out by condensing the para‐substituted benzaldehydes with benzidine to give the three‐ring compound, which was then condensed with terephthaldehyde to give the respective seven‐benzene‐ring oligomers. The oligomers were characterized by elemental analysis, electronic spectra, Fourier‐transform infrared and thermal analysis. The oligomers were used to investigate the effects of their molecular structure on their electronic spectra, as well as their thermal, electronic and electrical properties. The different conformers were reported and compared. The DC electrical conductivity variation of oligoazomethines was studied in the temperature range 300–500 K after annealing for 24 h at 100 °C and after doping with 5% I₂. An attempt was made to relate the DC electrical conductivity, electronic properties and thermal properties to the chain length, substituted groups and coplanarity. The fairly low conductivity obtained was attributed to the non‐linearity of the rings in the chain. The different groups (neutral, electron withdrawing or electron donating) attached at the ends of the oligomer showed no influence upon the conductivity of the different oligomers. The action of doping gave almost the same enhancement as that noticed in the case of a long‐chain polymer. The DC electrical conductivity was interpreted using the band energy model. The seven‐benzene‐ring oligomer gave the same DC electrical conductivity as the long‐chain polymer. Copyright © 2004 Society of Chemical Industry     

Synthesis,Characterization and Optoelectronic Properties of Dimeric and Polymeric Metallaynes Derived from 3,6-Bis(buta-1,3-diynyl)-9-butylcarbazole

A thermally stable platinum(II) polyyne polymer incorporating carbazole-based linking units, trans-[–Pt(PBu₃)₂C≡CC≡CRC≡CC≡C–] _n (R = 9-butylcarbazole-3,6-diyl), was prepared by polycondensation polymerization of trans-[PtCl₂(PBu₃)₂] with H–C≡CC≡CRC≡CC≡C–H. We report the optical absorption and photoluminescence spectra of this carbon-rich metallopolymer and compare its photophysics with its molecular dinuclear model complex trans-[Pt(Ph)(PEt₃)₂C≡CC≡CRC≡CC≡CPt(Ph)(PEt₃)₂] as well as the group 11 gold(I) congener, [(PPh₃)AuC≡CC≡CRC≡CC≡CAu(PPh₃)]. Characterization of the polymer and metal complexes was accomplished by FT-IR and NMR spectroscopies and FAB mass spectrometry. Our investigations showed that harvesting of the organic triplet emissions can be achieved by the heavy-atom effect of Pt and Au centers, which enables a very high efficiency of intersystem crossing from the S₁ singlet excited state to the T₁ triplet excited state. The influence of the metal and the C≡C chain length on the intersystem crossing rate and the spatial extent of singlet and triplet excitons is characterized. The present work indicates that high-energy triplet states intrinsically give more efficient phosphorescence in metal-containing diethynylcarbazole systems than in the corresponding bis(butadiynyl) congeners and can thus enhance the radiative decay pathway.Dedicated to Professor Richard J. Puddephatt in recognition of his outstanding contribution to inorganic and organometallic chemistry.     

The reaction thermodynamics of hydrogen sulfide decomposition into hydrogen and diatomic sulfur

To verify a hypothesis about the electronic state of diatomic gaseous sulfur formed during the low-temperature catalytic decomposition of hydrogen sulfide, we carried out some experiments to examine elemental sulfur dissociation. As shown, after heating at ～1000?K, elemental sulfur sealed in quartz ampoules with metal catalysts followed by quenching at room temperature did not produce any visible changes on solid sulfur. However, conversion of solid sulfur into gaseous diatomic sulfur can be realized via intermediate interaction of melted sulfur with hydrogen in the presence of Pt followed by decomposition of H₂S formed on the surface of the metal catalyst at room temperature. It is suggested that the conversion of the singlet sulfur atoms into the ground triplet state becomes feasible only on the surface of metal catalysts resulted from the dissociation of hydrogen sulfide into adsorbed atomic species.     

Star‐Shaped,Dendrimeric and Polymeric Triarylamines as Photoconductors and Hole Transport Materials for Electro‐Optical Applications

Recent developments in the synthesis and application of hole conducting oligomeric and polymeric triarylamines are reviewed. The materials are classified as Star‐shaped molecules, Spiros and dendrimers, Side‐chain polymers, and Main‐chain polymers and copolymers. This paper concentrates on the research results of our group on the synthesis of a variety of such compounds, their structure‐property relationship and their application in devices like organic light emitting diodes, solar cells and photorefractive systems. The thermal properties and electronic properties of these compounds were varied by changing the chemical structure and nature of substituents. In the case of low molecular weight star‐shaped molecules the glass transition temperature could be increased to above 140°C by suitable structural design. Similarly, for polymeric triarylamines the variation of glass transition temperature was achieved over a wide range from 92 to 237°C. This is especially necessary for the wide spectrum of applications of these materials as hole conductors in low‐T_g photorefractive composites to high‐T_g materials in OLEDs. Moreover, the electronic energy levels and the band gap in these compounds can be manipulated to optimize the hole injection or electron transfer or emission properties or even photocurrent generation to make them suitable for various applications. Especially, the concept of copolymerization with other functional monomers results in multifunctional copolymers with good hole injection and transport properties. The polymer networks involving triarylamine structures are not included in this Review, because this constitutes the subject‐matter of insoluble hole transport materials and will be published elsewhere.