Co-reporter:Daniel L. Crossley, Laura Urbano, Robert Neumann, Struan Bourke, Jennifer Jones, Lea Ann Dailey, Mark Green, Martin J. Humphries, Simon M. King, Michael L. Turner, and Michael J. Ingleson
ACS Applied Materials & Interfaces August 30, 2017 Volume 9(Issue 34) pp:28243-28243
Publication Date(Web):August 7, 2017
DOI:10.1021/acsami.7b08473
Post-polymerization modification of the donor–acceptor polymer, poly(9,9-dioctylfluorene-alt-benzothiadiazole), PF8-BT, by electrophilic C–H borylation is a simple method to introduce controllable quantities of near-infrared (near-IR) emitting chromophore units into the backbone of a conjugated polymer. The highly stable borylated unit possesses a significantly lower LUMO energy than the pristine polymer resulting in a reduction in the band gap of the polymer by up to 0.63 eV and a red shift in emission of more than 150 nm. Extensively borylated polymers absorb strongly in the deep red/near-IR and are highly emissive in the near-IR region of the spectrum in solution and solid state. Photoluminescence quantum yield (PLQY) values are extremely high in the solid state for materials with emission maxima ≥ 700 nm with PLQY values of 44% at 700 nm and 11% at 757 nm for PF8-BT with different borylation levels. This high brightness enables efficient solution processed near-IR emitting OLEDs to be fabricated and highly emissive borylated polymer loaded conjugated polymer nanoparticles (CPNPs) to be prepared. The latter are bright, photostable, low toxicity bioimaging agents that in phantom mouse studies show higher signal to background ratios for emission at 820 nm than the ubiquitous near-IR emissive bioimaging agent indocyanine green. This methodology represents a general approach for the post-polymerization functionalization of donor–acceptor polymers to reduce the band gap as confirmed by the C–H borylation of poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2c,2cc-diyl) (PF8TBT) resulting in a red shift in emission of >150 nm, thereby shifting the emission maximum to 810 nm.Keywords: bioimaging; C−H borylation; low band gap; near-infrared emission; post-polymerization modification;
Co-reporter:Dharam R. Kumar;Benjamin J. Lidster;Ralph W. Adams
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 20) pp:3186-3194
Publication Date(Web):2017/05/23
DOI:10.1039/C7PY00543A
This paper discusses the living nature of the ring opening metathesis polymerisation (ROMP) of alkoxy and alkyl substituted [2.2] paracyclophane-1,9-dienes (M1 and M2), initiated with Grubbs’ second and third generation catalysts (G2 and G3). The active ruthenium carbene chain ends present during the ROMP of these monomers have been identified by in situ1H and 31P NMR spectroscopy and the relative kinetics of the initiation and propagation reactions in the polymerisation determined for both G2 and G3 complexes. The apparent rate constants for initiation of both M1 and M2 using G3 are at least one order of magnitude larger than those determined for polymerisation using G2 and this leads to lower dispersity (Đm) polymers using the G3 catalyst as initiator. Complexation of the ruthenium centre in the active chain end by the oxygen of the alkoxy substituents in M1 is observed in the NMR spectra of the reaction and this leads to significantly slower rates of propagation than those observed for the alkyl derivative M2 using both G2 and G3 complexes. Although the polymerisation requires longer to reach full conversion for monomer M1 the slower propagation generally results in better control of the polymer molecular weight (lower Đm) as the ratio of apparent rate constants for initiation and propagation are larger than those determined for the ROMP of M2.
Co-reporter:Josue Ayuso Carrillo, Michael L. Turner, and Michael J. Ingleson
Journal of the American Chemical Society 2016 Volume 138(Issue 40) pp:13361-13368
Publication Date(Web):September 16, 2016
DOI:10.1021/jacs.6b07666
Thienyl di-N-methyliminodiacetic acid (MIDA) boronate esters are readily synthesized by electrophilic C–H borylation producing bench stable crystalline solids in good yield and excellent purity. Optimal conditions for the slow release of the boronic acid using KOH as the base in biphasic THF/water mixtures enables the thienyl MIDA boronate esters to be extremely effective homo-bifunctionalized (AA-type) monomers in Suzuki–Miyaura copolymerizations with dibromo-heteroarenes (BB-type monomers). A single polymerization protocol is applicable for the formation of five alternating thienyl copolymers that are (or are close analogues of) state of the art materials used in organic electronics. The five polymers were produced in excellent yields and with high molecular weights comparable to those produced using Stille copolymerization protocols. Therefore, thienyl di-MIDA boronate esters represent bench stable and low toxicity alternatives to highly toxic di-trimethylstannyl AA-type monomers that are currently ubiquitous in the synthesis of these important alternating copolymers.
Co-reporter:Benjamin J. Lidster, Dharam R. Kumar, Andrew M. Spring, Chin-Yang Yu, Madeleine Helliwell, James Raftery and Michael L. Turner
Organic & Biomolecular Chemistry 2016 vol. 14(Issue 25) pp:6079-6087
Publication Date(Web):01 Jun 2016
DOI:10.1039/C6OB00885B
[2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.
Co-reporter:Jonathan M. Behrendt, Jair A. Esquivel Guzman, Laura Purdie, Helen Willcock, John J. Morrison, Andrew B. Foster, Rachel K. O'Reilly, Mark C. McCairn, Michael L. Turner
Reactive and Functional Polymers 2016 Volume 107() pp:69-77
Publication Date(Web):October 2016
DOI:10.1016/j.reactfunctpolym.2016.08.006
Suzuki cross-coupling polymerisation of aryldibromides and aryldiboronate esters in a sodium dodecyl sulfate (SDS)-stabilised miniemulsion provides a versatile and direct route to fluorescent conjugated polymer nanoparticles (CPNs). These nanoparticles have a conjugated backbone based on poly(9,9-dioctylfluorene) (PFO), however, significant structural diversity is introduced by incorporation of electron withdrawing, heterocyclic comonomers (5–50 mol.%) in order to tune the emission wavelengths from blue to far-red/near-infrared. The robust nature of the polymerisation methodology allows for rapid assessment of the relationship between polymer composition, chain morphology and optical properties of the resultant CPNs. Moreover, the CPNs (after a simple and rapid purification step) can be used directly in fluorescence-based intracellular labelling experiments (in HCT116 cells), in which they display low cytotoxicity at biologically-useful concentrations.
Co-reporter:Daniel L. Crossley;Dr. Inigo Vitorica-Yrezabal;Dr. Martin J. Humphries; Michael L. Turner;Dr. Michael J. Ingleson
Chemistry - A European Journal 2016 Volume 22( Issue 35) pp:12439-12448
Publication Date(Web):
DOI:10.1002/chem.201602010
Abstract
Stille, Suzuki–Miyaura and Negishi cross-coupling reactions of bromine-functionalised borylated precursors enable the facile, high yielding, synthesis of borylated donor–acceptor materials that contain electron-rich aromatic units and/or extended effective conjugation lengths. These materials have large Stokes shifts, low LUMO energies, small band-gaps and significant fluorescence emission >700 nm in solution and when dispersed in a host polymer.
Co-reporter:D. L. Crossley, I. A. Cade, E. R. Clark, A. Escande, M. J. Humphries, S. M. King, I. Vitorica-Yrezabal, M. J. Ingleson and M. L. Turner
Chemical Science 2015 vol. 6(Issue 9) pp:5144-5151
Publication Date(Web):12 Jun 2015
DOI:10.1039/C5SC01800E
Electrophilic borylation using BCl3 and benzothiadiazole to direct the C–H functionalisation of an adjacent aromatic unit produces fused boracyclic materials with minimally changed HOMO energy levels but significantly reduced LUMO energy levels. In situ alkylation and arylation at boron using Al(alkyl)3 or Zn(aryl)2 is facile and affords boracycles that possess excellent stability towards protic solvents, including water, and display large bathochromic shifts leading to far red/NIR emission in the solid state with quantum yields of up to 34%. Solution fabricated OLEDs with far red/NIR electroluminescence are reported with EQEs > 0.4%.
Co-reporter:Josué Ayuso Carrillo, Michael J. Ingleson, and Michael L. Turner
Macromolecules 2015 Volume 48(Issue 4) pp:979-986
Publication Date(Web):February 10, 2015
DOI:10.1021/ma502542g
The synthesis of highly regioregular poly(3-hexylthiophene-2,5-diyl), rr-P3HT, by Suzuki–Miyaura polymerization is reported. The key N-methyliminodiacetic acid (MIDA) boronate ester thienyl monomer was synthesized using a one-pot multigram scale procedure, in high purity, and in good isolated yield (80%) by direct electrophilic borylation. Conditions for the hydrolysis of the MIDA protecting group and the polymerization reaction were investigated. The optimal procedure gave rr-P3HT with >98% HT couplings, excellent isolated yields (up to 94%), and polymer molecular weights up to Mn = 18.7 kDa and Mw = 42.7 kDa. The performance of the MIDA containing monomer was compared to that of the pinacol boronate ester under identical polymerization conditions, with the latter producing lower molecular weight polymers in reduced yield.
Co-reporter:Adam V. S. Parry;Kexin Lu;Daniel J. Tate;Barbara Urasinska-Wojcik;Dolores Caras-Quintero;Leszek A. Majewski
Advanced Functional Materials 2014 Volume 24( Issue 42) pp:6677-6683
Publication Date(Web):
DOI:10.1002/adfm.201401392
Self assembled monolayer field effect transistors (SAMFETs) are reported using a phenylene-thiophene containing semiconducting mesogen attached through a trichlorosilane anchoring group. Monolayer films, covalently attached to silicon dioxide substrates, form in less than 10 h from solution, thanks to the accelerated reaction of the trichlorosilane anchor. Devices exhibit mobilities as high as 1.7 × 10−2 cm2 V−1 s−1, currents of up to 15 μA (on/off current ratio of 106) with device yields close to unity over large areas for channel lengths up to 100 μm.
Co-reporter:Reiner Sebastian Sprick, Mario Hoyos, Marion Sofia Wrackmeyer, Adam Valentine Sheridan Parry, Iain Mark Grace, Colin Lambert, Oscar Navarro and Michael Lewis Turner
Journal of Materials Chemistry A 2014 vol. 2(Issue 32) pp:6520-6528
Publication Date(Web):12 Jun 2014
DOI:10.1039/C4TC00871E
Polytriarylamines with extended fused backbones are accessible by the coupling of anilines with dibromoarenes based on substituted indenofluorenes, diindenofluorenes, carbazoles and indolocarbazoles. The optical and electrochemical properties of these polymers show an increase in the HOMO energy levels and the onset of absorption on extending the length of the fused ring segment. The polymer derived from the indenofluorene unit shows the highest reported performance for a polytriarylamine in an OFET and this observation can be rationalized by DFT calculations of model oligomers that show higher calculated reorganization energies for the more extended diindenofluorene units.
Co-reporter:Benjamin J. Lidster, Jonathan M. Behrendt and Michael L. Turner
Chemical Communications 2014 vol. 50(Issue 80) pp:11867-11870
Publication Date(Web):18 Aug 2014
DOI:10.1039/C4CC05118A
Poly(p-phenylenevinylene)s (PPVs) with single reactive end groups have been prepared with high molecular weights, narrow polydispersities (ĐM) and excellent end functionality (f). PPVs functionalised with α-bromoester end groups are effective macroinitiators in the atom transfer radical polymerisation (ATRP) of methyl methacrylate (MMA).
Co-reporter:Duangratchaneekorn Muenmart, Andrew B. Foster, Alan Harvey, Ming-Tsz Chen, Oscar Navarro, Vinich Promarak, Mark C. McCairn, Jonathan M. Behrendt, and Michael L. Turner
Macromolecules 2014 Volume 47(Issue 19) pp:6531-6539
Publication Date(Web):September 18, 2014
DOI:10.1021/ma501402h
A range of stable emulsions of spherical and rod-like conjugated polymer nanoparticles (CPN) were synthesized via Suzuki−Miyaura cross-coupling reactions of 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester with a number of different dibromoarene monomers in xylene, stabilized in water by the nonionic surfactant, Triton X-102. High molar mass poly(9,9-dioctylfluorene) (PF8), poly(9,9-dioctylfluorene-alt-benzothiadiazole) (PF8BT), poly(9,9-dioctylfluorene-alt-4-sec-butylphenyldiphenylamine) (PF8TAA) and poly(9,9-dioctylfluorene-alt-bithiophene) (PF8T2) emulsions were obtained, at high overall conjugated polymer concentrations (up to 11,000 ppm), in the presence of the palladium complex, (IPr*)PdCl2(TEA) and base, tetraethylammonium hydroxide, in nitrogen atmosphere at 30 °C after 24–48 h. TEM analysis of the PF8 and PF8T2 emulsions revealed regular rod-like structures, up to 200 nm in length with aspect ratios of 4–5. PF8BT and PF8TAA formed spherical particles with diameters of between 20–40 nm in TEM analysis. UV–vis absorption spectra of the PF8 emulsions indicated high levels of ordered β-phase configuration (9–10%) in their respective nanoparticles. Absolute photoluminescence quantum yields (Φ) of 21–25% were recorded for these emulsions.
Co-reporter:Pompi Hazarika, Jonathan M. Behrendt, Linn Petersson, Christer Wingren, Michael L. Turner
Biosensors and Bioelectronics 2014 Volume 53() pp:82-89
Publication Date(Web):15 March 2014
DOI:10.1016/j.bios.2013.09.001
•The surface attachment of scFv antibodies to oxide surfaces can be patterned using a photo labile SAM.•Antibodies can be attached covalently or non-covalently and retain their biological activity.•Attached antibodies show excellent specificity for detection of target antigens in buffer and human serum.The immobilization of functional biomolecules to surfaces is a critical process for the development of biosensors for disease diagnostics. In this work we report the patterned attachment of single chain fragment variable (scFv) antibodies to the surface of metal oxides by the photodeprotection of self-assembled monolayers, using near-UV light. The photodeprotection step alters the functionality at the surface; revealing amino groups that are utilized to bind biomolecules in the exposed regions of the substrate only. The patterned antibodies are used for the detection of specific disease biomarker proteins in buffer and in complex samples such as human serum.
Co-reporter:Reiner Sebastian Sprick, Mario Hoyos, John James Morrison, Iain Mark Grace, Colin Lambert, Oscar Navarro and Michael Lewis Turner
Journal of Materials Chemistry A 2013 vol. 1(Issue 20) pp:3327-3336
Publication Date(Web):09 Apr 2013
DOI:10.1039/C3TC30368C
A library of triarylamine copolymers with 2,7-fluorene, 3,7-dibenzo[b,d]thiophene and 2,7-carbazole units incorporated in the polymer backbone is reported. The polymers were synthesised by using C–N coupling of anilines and dibromoarenes, catalysed by N-heterocyclic carbene complexes of palladium. The properties of the polymers were tuned by changing the nature of the fused ring structure and the substitution of the pendant benzene of the arylamine. The use of these polymers as the charge transporting layer of an OFET is demonstrated with the highest mobility found for polymers derived from 2,7-dibromo-9,9′-dioctylfluorene and 4-methoxy-2-methylaniline.
Co-reporter:Jonathan M. Behrendt, Andrew B. Foster, Mark C. McCairn, Helen Willcock, Rachel K. O'Reilly and Michael L. Turner
Journal of Materials Chemistry A 2013 vol. 1(Issue 20) pp:3297-3304
Publication Date(Web):04 Apr 2013
DOI:10.1039/C3TC30266K
Polyfluorenes with pendant alkoxysilyl groups have been used to prepare inorganic–organic composite nanoparticles (diameter = 80–220 nm) in which the conjugated polymer is dispersed within a silica matrix. Preparation of these nanoparticles is achieved by simultaneous nanoprecipitation of the conjugated polymer and hydrolysis/crosslinking of the alkoxysilyl groups under basic conditions. The composition of the nanocomposites is controlled by addition of an alkoxysilane monomer, tetramethylorthosilicate. The hybrid nanoparticles form highly stable dispersions in water and buffer (pH 9.2). The size of the nanoparticles can be tuned by varying the amount of the alkoxysilane monomer added during the nanoprecipitation process. Increasing the relative amount of alkoxysilane monomer also increases the proportion of polyfluorene chains that adopt the higher energy β-phase conformation within the resultant nanoparticles. Nanoparticles with the highest silica content were found to have increased photoluminescence quantum yields. This work provides a controllable method for optimisation of the photophysical properties of light-emitting conjugated polymer nanoparticles via a simple aqueous processing technique.
Co-reporter:Jonathan M. Behrendt, Yun Wang, Helen Willcock, Laura Wall, Mark C. McCairn, Rachel K. O'Reilly and Michael L. Turner
Polymer Chemistry 2013 vol. 4(Issue 5) pp:1333-1336
Publication Date(Web):17 Jan 2013
DOI:10.1039/C3PY21068E
Polyfluorenes with both alkyl and poly(ethylene glycol) (PEG) side-chains have been synthesised and processed into fluorescent nanoparticles via nanoprecipitation. The PEG/alkyl ratio is found to exert a significant influence over the size, polymer microstructure and optical properties of the resultant nanoparticles. This paves the way for a deeper understanding of how polymer structure can be manipulated to provide greater control over the nanoprecipitation process.
Co-reporter:Reiner Sebastian Sprick;Mario Hoyos;Ming-Tsz Chen;Michael Lewis Turner;Oscar Navarro
Journal of Polymer Science Part A: Polymer Chemistry 2013 Volume 51( Issue 22) pp:4904-4911
Publication Date(Web):
DOI:10.1002/pola.26919
ABSTRACT
The use of a highly active, air-, and moisture-stable N-heterocyclic carbene-palladium(II) complex for the polymerization of anilines and aryl dibromides or dichlorides by Buchwald-Hartwig coupling is presented. In comparison to previous catalytic systems, higher molecular weight polymers with improved yields were obtained in shorter reaction times. The first examples of fabrication of OFETs with polytriarylamines synthesized with aryl dichlorides and anilines are also presented. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4904–4911
Co-reporter:Masaki Horie, Jeff Kettle, Chin-Yang Yu, Leszek A. Majewski, Shu-Wei Chang, James Kirkpatrick, Sachetan M. Tuladhar, Jenny Nelson, Brian R. Saunders and Michael L. Turner
Journal of Materials Chemistry A 2012 vol. 22(Issue 2) pp:381-389
Publication Date(Web):03 Nov 2011
DOI:10.1039/C1JM12449H
Conjugated oligomers with various ratios of cyclopentadithiophene (CPDT) to benzothiadiazole (BT) repeating units are reported. These oligomers can be polymerised to high molecular weight polymers (Mn > 100k) by oxidative polymerisation using iron(III)chloride. The electronic properties of these materials were examined by cyclic voltammetry and UV-vis spectroscopy and the results compared to those calculated using density functional theory (DFT). Polymers with optimum ratios of CPDT:BT (2:1) units show hole mobilities in excess of 10−2 cm2 V−1 s−1 as the active layer in organic field effect transistors (OFETs). Bulk heterojunction organic photovoltaic (OPV) devices of these polymers with PCBM as the electron acceptor show a power conversion efficiency of 2.1% when processed in the absence of any additives. The reported OFET performance is significantly higher than the parent PCPDTBT alternating copolymer (CPDT:BT = 1:1) and also shows a moderate improvement in OPV performance.
Co-reporter:Matthew T. Levick, Susannah C. Coote, Iain Grace, Colin Lambert, Michael L. Turner, and David J. Procter
Organic Letters 2012 Volume 14(Issue 22) pp:5744-5747
Publication Date(Web):October 30, 2012
DOI:10.1021/ol302748h
The introduction and removal of a phase tag have been used to trigger cyclization events in a new synthesis of benzo[b]carbazoles. The approach has been exploited in a tag-assisted approach to new benzo[b]carbazole end-capped oligothiophenes for preliminary evaluation as semiconductors.
Co-reporter:Mario Hoyos;Reiner Sebastian Sprick;Chao Wang;Michael Lewis Turner;Oscar Navarro
Journal of Polymer Science Part A: Polymer Chemistry 2012 Volume 50( Issue 20) pp:4155-4160
Publication Date(Web):
DOI:10.1002/pola.26239
Co-reporter:Reiner Sebastian Sprick, Mario Hoyos, Oscar Navarro, Michael Lewis Turner
Reactive and Functional Polymers 2012 72(5) pp: 337-340
Publication Date(Web):May 2012
DOI:10.1016/j.reactfunctpolym.2012.02.008
Co-reporter:Dr. Chin-Yang Yu;Dr. Madeleine Helliwell;Dr. James Raftery; Michael L. Turner
Chemistry - A European Journal 2011 Volume 17( Issue 25) pp:6991-6997
Publication Date(Web):
DOI:10.1002/chem.201003147
Abstract
Tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes can be prepared in three steps from dithia[3.3]paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds can be separated by fractional crystallization. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain. Reaction of these diastereomers with the second generation Grubbs catalyst shows that only the pseudo-geminal isomer can be ring opened to give cis,trans-distrylbenzenes. The origin of this selectivity is discussed and the photoisomerization of the as-formed cis,trans-product to the all trans isomer is demonstrated.
Co-reporter:Jonathan M. Behrendt, Michael Benstead, Adam Chaplin, Brian Wilson, and Michael L. Turner
Macromolecules 2011 Volume 44(Issue 22) pp:9054-9056
Publication Date(Web):October 21, 2011
DOI:10.1021/ma201580d
Co-reporter:Masaki Horie, Leszek A. Majewski, Michael J. Fearn, Chin-Yang Yu, Yi Luo, Aimin Song, Brian R. Saunders and Michael L. Turner
Journal of Materials Chemistry A 2010 vol. 20(Issue 21) pp:4347-4355
Publication Date(Web):20 Apr 2010
DOI:10.1039/B924126D
A series of cyclopentadithiophene based polymers have been synthesized by oxidative polymerisation or palladium-catalyzed coupling reactions. Polymers have been prepared with backbones containing benzothiadiazole, benzoxadiazole, 2,2′-bithiophene, phenyl and fluorene units. The backbone structure is shown to have a large effect on the film morphology, and the optical and electrochemical properties in solution and the solid state. We show that the polymer composition can be used to tune the band gap over the entire visible spectrum. Spin-coated films of these polymers have been used as the active layer of organic field effect transistors and hole mobilities up to 3.7 × 10−3 cm2 V−1 s−1 have been measured under ambient conditions.
Co-reporter:Mark C. McCairn, Theo Kreouzis and Michael L. Turner
Journal of Materials Chemistry A 2010 vol. 20(Issue 10) pp:1999-2006
Publication Date(Web):25 Jan 2010
DOI:10.1039/B922714H
A series of π-conjugated 2,5-di-thiophene-[1,3,4]thiadiazole based pentamers have been synthesised by microwave promoted palladium catalysed cross-coupling reactions. The aromatic groups that terminate each pentamer have a profound effect on the observed optical, electrochemical and liquid crystalline properties. Substitution of progressively less electron rich aromatic groups at the periphery of the pentamers decreased the energy gap between the ground state and the first excited state and also lowered the energy of the frontier orbitals sufficiently to impede oxidation and facilitate reduction. The thermotropic calamitic mesogen, 2,5-bis-[5-(4-hexyl-phenyl)-thiophen-2-yl]-[1,3,4]thiadiazole, 7 showed non-dispersive ambipolar charge transport in the nematic, smectic and crystalline phases. The charge mobility increased concomitantly with increasing molecular order of the mesophase to a maximum in the highest ordered smectic phase (µhole ≈ 4 × 10−3 cm2 V−1 s−1, µelectron ≈ 8 × 10−3 cm2 V−1 s−1).
Co-reporter:Chin-Yang Yu, Masaki Horie, Andrew M. Spring, Kim Tremel and Michael L. Turner
Macromolecules 2010 Volume 43(Issue 1) pp:222-232
Publication Date(Web):November 25, 2009
DOI:10.1021/ma901966g
p-Phenylenevinylene-2,5-diethylhexyloxy-p-phenylenevinylene and m-phenylenevinylene-2,5-diethylhexyloxy-p-phenylenevinylene homopolymers (3 and 4) have been prepared by the ring-opening metathesis polymerization (ROMP) of strained cyclophanedienes, initiated by the second generation Grubbs catalyst. The as-formed polymers have a backbone of alternating cis- and trans-vinylene linkages due to the opening of only one vinylene of the cyclophanediene. Irradiation with UV light results in an isomerization to an all-trans-vinylene microstructure for all polymers. The polymer chain ends remain active after complete consumption of the cyclophanediene, and block copolymers can be prepared by addition of further cyclophanediene. The optical and electronic properties of the homopolymers and block copolymers are reported.
Co-reporter:Masaki Horie, I.-Wen Shen, Sachetan M. Tuladhar, Henry Leventis, Saif A. Haque, Jenny Nelson, Brian R. Saunders, Michael L. Turner
Polymer 2010 Volume 51(Issue 7) pp:1541-1547
Publication Date(Web):24 March 2010
DOI:10.1016/j.polymer.2010.01.049
Poly(3,4-dioctylthienylenevinylene) (PDOTV) was synthesised by ring-opening metathesis polymerization (ROMP) with controlled molecular weight. PDOTV has been used to fabricate organic photovoltaic devices in combination with phenyl C61-butyric acid methyl ester (PCBM) for the first time. The devices show power conversion efficiency up to 0.18%. Optimal device performance was found at a film thickness of 100 nm and a ratio of PCBM to PTV of 2:1. External quantum efficiency (EQE) measurements, transient absorption spectroscopy and morphology studies were carried out to establish factors governing photovoltaic performance. These results suggest that the efficiency values for the devices were limited by the hole mobility and unexpected phase separation within the blend. Nevertheless, the results show that ROMP is a viable, alternative, synthetic strategy for preparing PTV donors for use in bulk heterojunction OPVs.
Co-reporter:Andrew M. Spring, Chin-Yang Yu, Masaki Horie and Michael L. Turner
Chemical Communications 2009 (Issue 19) pp:2676-2678
Publication Date(Web):25 Mar 2009
DOI:10.1039/B901075K
Excellent control in the synthesis of MEH-PPV can be achieved by microwave assisted, ring-opening metathesis polymerisation (ROMP) of [2.2]paracyclophanedienes.
Co-reporter:Chin-Yang Yu;James W. Kingsley;David G. Lidzey
Macromolecular Rapid Communications 2009 Volume 30( Issue 22) pp:1889-1892
Publication Date(Web):
DOI:10.1002/marc.200900345
Co-reporter:Masaki Horie, Yi Luo, John J. Morrison, Leszek A. Majewski, Aimin Song, Brian R. Saunders and Michael L. Turner
Journal of Materials Chemistry A 2008 vol. 18(Issue 43) pp:5230-5236
Publication Date(Web):30 Sep 2008
DOI:10.1039/B808840C
Triarylamine polymers can be rapidly assembled by microwave-assisted amination of aryldibromides. A series of polymers are reported with backbones containing 4,4′-biphenyl, 2.9-fluorene and 3,6-carbazole repeating units. These polymers have been used to fabricate organic field-effect transistors. The devices show very stable operation under ambient conditions and p-type mobilities up to 2.3 × 10−3 cm2V−1 s−1, close to the highest mobility reported to date for this class of amorphous semiconductors.
Co-reporter:J. C. Maunoury;J. R. Howse;M. L. Turner
Advanced Materials 2007 Volume 19(Issue 6) pp:805-809
Publication Date(Web):9 MAR 2007
DOI:10.1002/adma.200602859
Melt-processing of 5,5′-bis(4-hexylphenyl)-2,2′-bithiophene leads to a favorable morphology of the conjugated liquid crystal in the channel of an OFET (see figure) and a fivefold improvement of the mobility over that found for conventional devices fabricated by evaporation. This process does not require solvents or vacuum-deposition processes.
Co-reporter:Mark C. McCairn;John J. Morrison;I-Wen Shen
Macromolecular Rapid Communications 2007 Volume 28(Issue 4) pp:449-455
Publication Date(Web):21 FEB 2007
DOI:10.1002/marc.200600720
A new synthetic route to polytriarylamines by microwave-assisted palladium-catalysed amination between 2,4-dimethylaniline and 4,4′-dibromobiphenyl is reported. The use of microwave heating significantly reduces the polymerisation time from days to around five minutes when conducted at 100 °C. However, prolonged microwave irradiation (20 min) can cause chain degradation of these polymers. Reactive amino and bromo end-groups can be removed by sequential reaction with 4-bromoanisole and diethylamine to generate polytriarylamines that are suitable for the fabrication of organic electronic devices.
Co-reporter:Franklin Jaramillo-Isaza and Michael L. Turner
Journal of Materials Chemistry A 2006 vol. 16(Issue 1) pp:83-89
Publication Date(Web):05 Oct 2005
DOI:10.1039/B511349K
Conjugated oligomers based on fluorene, fluorenone and thiophene derivatives have been prepared by parallel synthesis using the Suzuki cross-coupling reaction. These oligomers can be used as models of the corresponding fluorene copolymers and their structures were correlated with the observed optical and electrochemical behaviour. The long wavelength absorption bands observed for oligomers that contain fluorenone or cyclopentadithiophene units were assigned to an allowed π–π* transition associated with the carbonyl containing monomer unit. In addition the photoluminescence efficiency and the concentration dependence of the long wavelength emission band (>525 nm) for these materials strongly suggests that it can be attributed to emission involving fluorenone-based excimers.
Co-reporter:Brian Wilson;Elizabeth C. Harper;Paolo Coppo;Ian Teasdale
Macromolecular Rapid Communications 2006 Volume 27(Issue 23) pp:2032-2037
Publication Date(Web):27 NOV 2006
DOI:10.1002/marc.200600586
Summary: Macrocyclic phenyl ether ketones were prepared via pseudo high dilution condensation. Irradiation of these rings with UV light in a solution containing isopropyl alcohol as hydrogen donor resulted in a photo-induced reduction of benzophenone to benzopinacol and the formation linked macrocycles. These rings can be heated to undergo ring-opening polymerization and produce a polymer network or they can be added to a polycondensation reaction to prepare poly(ether ether ketones) with variable degrees of cross-linking.
Co-reporter:Chin-Yang Yu
Angewandte Chemie 2006 Volume 118(Issue 46) pp:
Publication Date(Web):24 OCT 2006
DOI:10.1002/ange.200602863
Die Ringöffnung substituierter Cyclophandiene durch Ruthenium-Metathesekatalysatoren führt zu löslichen Phenylenvinylen-Homopolymeren mit definiertem Molekulargewicht und alternierender cis,trans-Verknüpfung (siehe Bild, R=OC8H17). Dass es sich bei dieser Reaktion um eine lebende Polymerisation handelt, zeigt eine kontrollierte Kettenverlängerung.
Co-reporter:Chin-Yang Yu
Angewandte Chemie International Edition 2006 Volume 45(Issue 46) pp:
Publication Date(Web):24 OCT 2006
DOI:10.1002/anie.200602863
Ring opening of substituted cyclophanedienes by ruthenium-based metathesis catalysts gives soluble phenylenevinylene homopolymers of well-defined molecular weight with an alternating cis-trans microstructure (see picture, R=OC8H17). The living character of this polymerization is demonstrated by controlled chain extension.
Co-reporter:Paolo Coppo and Michael L. Turner
Journal of Materials Chemistry A 2005 vol. 15(Issue 11) pp:1123-1133
Publication Date(Web):19 Jan 2005
DOI:10.1039/B412143K
A wide variety of electroactive materials are accessible based on a cyclopentadithiophene skeleton. This Feature Article describes the synthesis of these materials, examines their intriguing properties (i.e. high electrical conductivity, low band-gap and extended π-conjugation) and discusses the complex relationship between structure and function in this system.
Co-reporter:Andrew M. Spring, Chin-Yang Yu, Masaki Horie and Michael L. Turner
Chemical Communications 2009(Issue 19) pp:NaN2678-2678
Publication Date(Web):2009/03/25
DOI:10.1039/B901075K
Excellent control in the synthesis of MEH-PPV can be achieved by microwave assisted, ring-opening metathesis polymerisation (ROMP) of [2.2]paracyclophanedienes.
Co-reporter:Masaki Horie, Yi Luo, John J. Morrison, Leszek A. Majewski, Aimin Song, Brian R. Saunders and Michael L. Turner
Journal of Materials Chemistry A 2008 - vol. 18(Issue 43) pp:NaN5236-5236
Publication Date(Web):2008/09/30
DOI:10.1039/B808840C
Triarylamine polymers can be rapidly assembled by microwave-assisted amination of aryldibromides. A series of polymers are reported with backbones containing 4,4′-biphenyl, 2.9-fluorene and 3,6-carbazole repeating units. These polymers have been used to fabricate organic field-effect transistors. The devices show very stable operation under ambient conditions and p-type mobilities up to 2.3 × 10−3 cm2V−1 s−1, close to the highest mobility reported to date for this class of amorphous semiconductors.
Co-reporter:Reiner Sebastian Sprick, Mario Hoyos, John James Morrison, Iain Mark Grace, Colin Lambert, Oscar Navarro and Michael Lewis Turner
Journal of Materials Chemistry A 2013 - vol. 1(Issue 20) pp:NaN3336-3336
Publication Date(Web):2013/04/09
DOI:10.1039/C3TC30368C
A library of triarylamine copolymers with 2,7-fluorene, 3,7-dibenzo[b,d]thiophene and 2,7-carbazole units incorporated in the polymer backbone is reported. The polymers were synthesised by using C–N coupling of anilines and dibromoarenes, catalysed by N-heterocyclic carbene complexes of palladium. The properties of the polymers were tuned by changing the nature of the fused ring structure and the substitution of the pendant benzene of the arylamine. The use of these polymers as the charge transporting layer of an OFET is demonstrated with the highest mobility found for polymers derived from 2,7-dibromo-9,9′-dioctylfluorene and 4-methoxy-2-methylaniline.
Co-reporter:Masaki Horie, Leszek A. Majewski, Michael J. Fearn, Chin-Yang Yu, Yi Luo, Aimin Song, Brian R. Saunders and Michael L. Turner
Journal of Materials Chemistry A 2010 - vol. 20(Issue 21) pp:NaN4355-4355
Publication Date(Web):2010/04/20
DOI:10.1039/B924126D
A series of cyclopentadithiophene based polymers have been synthesized by oxidative polymerisation or palladium-catalyzed coupling reactions. Polymers have been prepared with backbones containing benzothiadiazole, benzoxadiazole, 2,2′-bithiophene, phenyl and fluorene units. The backbone structure is shown to have a large effect on the film morphology, and the optical and electrochemical properties in solution and the solid state. We show that the polymer composition can be used to tune the band gap over the entire visible spectrum. Spin-coated films of these polymers have been used as the active layer of organic field effect transistors and hole mobilities up to 3.7 × 10−3 cm2 V−1 s−1 have been measured under ambient conditions.
Co-reporter:Masaki Horie, Jeff Kettle, Chin-Yang Yu, Leszek A. Majewski, Shu-Wei Chang, James Kirkpatrick, Sachetan M. Tuladhar, Jenny Nelson, Brian R. Saunders and Michael L. Turner
Journal of Materials Chemistry A 2012 - vol. 22(Issue 2) pp:
Publication Date(Web):
DOI:10.1039/C1JM12449H
Co-reporter:Benjamin J. Lidster, Jonathan M. Behrendt and Michael L. Turner
Chemical Communications 2014 - vol. 50(Issue 80) pp:NaN11870-11870
Publication Date(Web):2014/08/18
DOI:10.1039/C4CC05118A
Poly(p-phenylenevinylene)s (PPVs) with single reactive end groups have been prepared with high molecular weights, narrow polydispersities (ĐM) and excellent end functionality (f). PPVs functionalised with α-bromoester end groups are effective macroinitiators in the atom transfer radical polymerisation (ATRP) of methyl methacrylate (MMA).
Co-reporter:D. L. Crossley, I. A. Cade, E. R. Clark, A. Escande, M. J. Humphries, S. M. King, I. Vitorica-Yrezabal, M. J. Ingleson and M. L. Turner
Chemical Science (2010-Present) 2015 - vol. 6(Issue 9) pp:NaN5151-5151
Publication Date(Web):2015/06/12
DOI:10.1039/C5SC01800E
Electrophilic borylation using BCl3 and benzothiadiazole to direct the C–H functionalisation of an adjacent aromatic unit produces fused boracyclic materials with minimally changed HOMO energy levels but significantly reduced LUMO energy levels. In situ alkylation and arylation at boron using Al(alkyl)3 or Zn(aryl)2 is facile and affords boracycles that possess excellent stability towards protic solvents, including water, and display large bathochromic shifts leading to far red/NIR emission in the solid state with quantum yields of up to 34%. Solution fabricated OLEDs with far red/NIR electroluminescence are reported with EQEs > 0.4%.
Co-reporter:Benjamin J. Lidster, Dharam R. Kumar, Andrew M. Spring, Chin-Yang Yu, Madeleine Helliwell, James Raftery and Michael L. Turner
Organic & Biomolecular Chemistry 2016 - vol. 14(Issue 25) pp:NaN6087-6087
Publication Date(Web):2016/06/01
DOI:10.1039/C6OB00885B
[2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.
Co-reporter:Reiner Sebastian Sprick, Mario Hoyos, Marion Sofia Wrackmeyer, Adam Valentine Sheridan Parry, Iain Mark Grace, Colin Lambert, Oscar Navarro and Michael Lewis Turner
Journal of Materials Chemistry A 2014 - vol. 2(Issue 32) pp:NaN6528-6528
Publication Date(Web):2014/06/12
DOI:10.1039/C4TC00871E
Polytriarylamines with extended fused backbones are accessible by the coupling of anilines with dibromoarenes based on substituted indenofluorenes, diindenofluorenes, carbazoles and indolocarbazoles. The optical and electrochemical properties of these polymers show an increase in the HOMO energy levels and the onset of absorption on extending the length of the fused ring segment. The polymer derived from the indenofluorene unit shows the highest reported performance for a polytriarylamine in an OFET and this observation can be rationalized by DFT calculations of model oligomers that show higher calculated reorganization energies for the more extended diindenofluorene units.
Co-reporter:Mark C. McCairn, Theo Kreouzis and Michael L. Turner
Journal of Materials Chemistry A 2010 - vol. 20(Issue 10) pp:NaN2006-2006
Publication Date(Web):2010/01/25
DOI:10.1039/B922714H
A series of π-conjugated 2,5-di-thiophene-[1,3,4]thiadiazole based pentamers have been synthesised by microwave promoted palladium catalysed cross-coupling reactions. The aromatic groups that terminate each pentamer have a profound effect on the observed optical, electrochemical and liquid crystalline properties. Substitution of progressively less electron rich aromatic groups at the periphery of the pentamers decreased the energy gap between the ground state and the first excited state and also lowered the energy of the frontier orbitals sufficiently to impede oxidation and facilitate reduction. The thermotropic calamitic mesogen, 2,5-bis-[5-(4-hexyl-phenyl)-thiophen-2-yl]-[1,3,4]thiadiazole, 7 showed non-dispersive ambipolar charge transport in the nematic, smectic and crystalline phases. The charge mobility increased concomitantly with increasing molecular order of the mesophase to a maximum in the highest ordered smectic phase (µhole ≈ 4 × 10−3 cm2 V−1 s−1, µelectron ≈ 8 × 10−3 cm2 V−1 s−1).
Co-reporter:Jonathan M. Behrendt, Andrew B. Foster, Mark C. McCairn, Helen Willcock, Rachel K. O'Reilly and Michael L. Turner
Journal of Materials Chemistry A 2013 - vol. 1(Issue 20) pp:NaN3304-3304
Publication Date(Web):2013/04/04
DOI:10.1039/C3TC30266K
Polyfluorenes with pendant alkoxysilyl groups have been used to prepare inorganic–organic composite nanoparticles (diameter = 80–220 nm) in which the conjugated polymer is dispersed within a silica matrix. Preparation of these nanoparticles is achieved by simultaneous nanoprecipitation of the conjugated polymer and hydrolysis/crosslinking of the alkoxysilyl groups under basic conditions. The composition of the nanocomposites is controlled by addition of an alkoxysilane monomer, tetramethylorthosilicate. The hybrid nanoparticles form highly stable dispersions in water and buffer (pH 9.2). The size of the nanoparticles can be tuned by varying the amount of the alkoxysilane monomer added during the nanoprecipitation process. Increasing the relative amount of alkoxysilane monomer also increases the proportion of polyfluorene chains that adopt the higher energy β-phase conformation within the resultant nanoparticles. Nanoparticles with the highest silica content were found to have increased photoluminescence quantum yields. This work provides a controllable method for optimisation of the photophysical properties of light-emitting conjugated polymer nanoparticles via a simple aqueous processing technique.
![Poly[[2,5-bis[(2-ethylhexyl)oxy]-1,4-phenylene]-1,2-ethenediyl-1,4-phenyl
ene-1,2-ethenediyl]](http://img.cochemist.com/ccimg/466700/466696-87-7.png)
![Poly[[2,5-bis[(2-ethylhexyl)oxy]-1,4-phenylene]-1,2-ethenediyl-1,4-phenyl
ene-1,2-ethenediyl]](http://img.cochemist.com/ccimg/466700/466696-87-7_b.png)
![Poly[[[4-(1-methylpropyl)phenyl]imino]-1,4-phenylene(9,9-dioctyl-9H-fluo
rene-2,7-diyl)-1,4-phenylene]](/data/chemimg/3109700/220797-16-0.png)
![Poly[[[4-(1-methylpropyl)phenyl]imino]-1,4-phenylene(9,9-dioctyl-9H-fluo
rene-2,7-diyl)-1,4-phenylene]](/data/chemimg/3109700/220797-16-0_b.png)
![[2,2':7',2''-Ter-9H-fluoren]-9'-one, 9,9,9'',9''-tetraoctyl-](/data/chemimg/3509300/875440-98-5.png)
![[2,2':7',2''-Ter-9H-fluoren]-9'-one, 9,9,9'',9''-tetraoctyl-](/data/chemimg/3509300/875440-98-5_b.png)
![[2,2':7',2''-Ter-9H-fluoren]-9-one, 9',9',9'',9''-tetraoctyl-](http://img.cochemist.com/ccimg/875500/875441-00-2.png)
![[2,2':7',2''-Ter-9H-fluoren]-9-one, 9',9',9'',9''-tetraoctyl-](http://img.cochemist.com/ccimg/875500/875441-00-2_b.png)
![Poly[[(4-fluorophenyl)imino][1,1'-biphenyl]-4,4'-diyl]](http://img.cochemist.com/ccimg/618200/618108-64-8.png)
![Poly[[(4-fluorophenyl)imino][1,1'-biphenyl]-4,4'-diyl]](http://img.cochemist.com/ccimg/618200/618108-64-8_b.png)
![Stannane, (3,3'-dihexyl[2,2'-bithiophene]-5,5'-diyl)bis[tributyl-](http://img.cochemist.com/ccimg/538400/538376-38-4.png)
![Stannane, (3,3'-dihexyl[2,2'-bithiophene]-5,5'-diyl)bis[tributyl-](http://img.cochemist.com/ccimg/538400/538376-38-4_b.png)
![Poly[[2,5-bis(octyloxy)-1,4-phenylene]-1,2-ethenediyl]](http://img.cochemist.com/ccimg/133100/133069-19-9.png)
![Poly[[2,5-bis(octyloxy)-1,4-phenylene]-1,2-ethenediyl]](http://img.cochemist.com/ccimg/133100/133069-19-9_b.png)
![BENZO[B]THIOPHENE, 2-PENTYL-](http://img.cochemist.com/ccimg/90000/89969-72-2.png)
![BENZO[B]THIOPHENE, 2-PENTYL-](http://img.cochemist.com/ccimg/90000/89969-72-2_b.png)
![[2,2':7',2''-TER-9H-FLUORENE]-9,9''-DIONE, 9',9'-DIOCTYL-](http://img.cochemist.com/ccimg/875500/875440-99-6.png)
![[2,2':7',2''-TER-9H-FLUORENE]-9,9''-DIONE, 9',9'-DIOCTYL-](http://img.cochemist.com/ccimg/875500/875440-99-6_b.png)
![4,4-di(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b]dithiophene](http://img.cochemist.com/ccimg/365600/365547-20-2.png)
![4,4-di(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b]dithiophene](http://img.cochemist.com/ccimg/365600/365547-20-2_b.png)
![2,6-Dibromo-4H-cyclopenta[1,2-b:5,4-b']dithiophen-4-one](http://img.cochemist.com/ccimg/636600/636588-79-9.png)
![2,6-Dibromo-4H-cyclopenta[1,2-b:5,4-b']dithiophen-4-one](http://img.cochemist.com/ccimg/636600/636588-79-9_b.png)
![3,7-Dibromodibenzo[b,d]thiophene](http://img.cochemist.com/ccimg/83900/83834-10-0.png)
![3,7-Dibromodibenzo[b,d]thiophene](http://img.cochemist.com/ccimg/83900/83834-10-0_b.png)
![3,9-Dibromo-5,11-dioctyl-5,11-dihydroindolo[3,2-b]carbazole](http://img.cochemist.com/ccimg/951400/951307-27-0.png)
![3,9-Dibromo-5,11-dioctyl-5,11-dihydroindolo[3,2-b]carbazole](http://img.cochemist.com/ccimg/951400/951307-27-0_b.png)
![Poly[[2,2'-bithiophene]-5,5'-diyl(9,9-dioctyl-9H-fluorene-2,7-diyl)]](http://img.cochemist.com/ccimg/210400/210347-56-1.png)
![Poly[[2,2'-bithiophene]-5,5'-diyl(9,9-dioctyl-9H-fluorene-2,7-diyl)]](http://img.cochemist.com/ccimg/210400/210347-56-1_b.png)
![METHANESULFONIC ACID;2-[2-(2-METHOXYETHOXY)ETHOXY]ETHANOL](http://img.cochemist.com/ccimg/74700/74654-05-0.png)
![METHANESULFONIC ACID;2-[2-(2-METHOXYETHOXY)ETHOXY]ETHANOL](http://img.cochemist.com/ccimg/74700/74654-05-0_b.png)
![Benzo[b]thiophene, 3-ethyl-2-methyl-](http://img.cochemist.com/ccimg/61700/61612-04-2.png)
![Benzo[b]thiophene, 3-ethyl-2-methyl-](http://img.cochemist.com/ccimg/61700/61612-04-2_b.png)
![2,8-DIBROMO-6,6,12,12-TETRAOCTYLINDENO[1,2-B]FLUORENE](/data/chemimg/487900/264281-45-0.png)
![2,8-DIBROMO-6,6,12,12-TETRAOCTYLINDENO[1,2-B]FLUORENE](/data/chemimg/487900/264281-45-0_b.png)
![6,6,12,12-TETRAOCTYLINDENO[1,2-B]FLUORENE](http://img.cochemist.com/ccimg/264300/264281-52-9.png)
![6,6,12,12-TETRAOCTYLINDENO[1,2-B]FLUORENE](http://img.cochemist.com/ccimg/264300/264281-52-9_b.png)
![4H-Cyclopenta[2,1-b:3,4-b']dithiophene, 2,6-dibromo-4,4-bis(2-ethylhexyl)-](/data/chemimg/542100/365547-21-3.png)
![4H-Cyclopenta[2,1-b:3,4-b']dithiophene, 2,6-dibromo-4,4-bis(2-ethylhexyl)-](/data/chemimg/542100/365547-21-3_b.png)
![Poly[2,7-(9,9-di-octyl-fluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole]](/data/chemimg/133300/782469-77-6.png)
![Poly[2,7-(9,9-di-octyl-fluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole]](/data/chemimg/133300/782469-77-6_b.png)
![Stannane, 1,1'-thieno[3,2-b]thiophene-2,5-diylbis[1,1,1-tributyl-](/data/chemimg/120600/909280-85-9.png)
![Stannane, 1,1'-thieno[3,2-b]thiophene-2,5-diylbis[1,1,1-tributyl-](/data/chemimg/120600/909280-85-9_b.png)
![Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,7-diyl)]](/data/chemimg/107700/210347-52-7.png)
![Poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,7-diyl)]](/data/chemimg/107700/210347-52-7_b.png)
![2,5-Bis(trimethylstannyl)thieno[3,2-b]thiophene](http://img.cochemist.com/ccimg/470000/469912-82-1.png)
![2,5-Bis(trimethylstannyl)thieno[3,2-b]thiophene](http://img.cochemist.com/ccimg/470000/469912-82-1_b.png)
![Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]](/data/chemimg/102300/920515-34-0.png)
![Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]](/data/chemimg/102300/920515-34-0_b.png)
![Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]](http://img.cochemist.com/ccimg/138200/138184-36-8.png)
![Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]](http://img.cochemist.com/ccimg/138200/138184-36-8_b.png)
![Stannane, [2,2'-bithiophene]-5,5'-diylbis[tributyl-](/data/chemimg/105800/171290-94-1.png)
![Stannane, [2,2'-bithiophene]-5,5'-diylbis[tributyl-](/data/chemimg/105800/171290-94-1_b.png)
![Allylchloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]palladium(II)](/data/chemimg/45500/478980-03-9.png)
![Allylchloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]palladium(II)](/data/chemimg/45500/478980-03-9_b.png)
