Effect of conjugated core building block dibenzo[a,c]phenazine unit on π‐conjugated electrochromic polymers: Red‐shifted absorption

A comparative investigation was undertaken for the electrosynthesis and electrochemical properties of three different electroactive polymers having a conjugated core building block, dibenzo[a,c]phenazine. A series of monomers has been synthesized as regards to thiophene based units; thiophene, 3‐hexyl thiophene, and 3,4‐ethylenedioxythiophene. The effects of different donor substituents on the polymers' electrochemical properties were examined by cyclic voltammetry. Introducing highly electron‐donating (ethylene dioxy) group to the monomer enables solubility while also lowering the oxidation potential. The planarity of the monomer unit enhances π‐stacking and consequently lowering the E_g from 2.4 eV (PHTP) to 1.7 (PTBP). Cyclic voltammetry and spectroelectrochemical measurements revealed that 2,7‐bis(4‐hexylthiophen‐2‐yl)dibenzo[a,c]phenazine (HTP) and 2,7‐bis(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐5‐yl)dibenzo[a,c]phenazine (TBP) possessed electrochromic behavior. The colorimetry analysis revealed that while PTBP have a color change from red to blue, PHTP has yellow color at neutral state and blue color at oxidized state. Hence the presence of the phenazine derivative as the acceptor unit causes a red shift in the polymers' absorption to have a blue color. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1714–1720, 2010     

Synthesis and electronic, photophysical, and electrochemical properties of a series of thienylcarbazoles

A series of thienylcarbazoles were synthesized by Suzuki-Miyaura and Ullmann coupling reactions. In these compounds, the 2-thienyl or 2,2'-bithiophen-5-yl group is connected at the N-, 1,8-, 3,6-, 2,7-, 2,7,N-, or 1,8,N-positions of the carbazole ring. The effects of structural variations on their electronic, photophysical, and electrochemical properties were explored by UV-vis and fluorescence spectroscopies, cyclic voltammetry (CV), and DFT calculations in evaluation of their potential as material components. The thienyl substituents at the 2,7-positions in 4, 5, and 10 are responsible for a high degree of π-conjugation and strong emission with fluorescence quantum yields up to 0.61. The CV on a series of thienylcarbazoles revealed a good electron-donating ability of 3,6-substituted carbazoles 3 and 9. The number of thiophene units was found to affect the extent of π-conjugation, the resulting HOMO-LUMO gaps, and fluorescence efficiency. The crystal structures of 5 and 9 were also disclosed.     

Synthesis and Properties of Fused‐Ring‐Expanded Porphyrins that were Core‐Modified with Group 16 Heteroatoms

The synthesis of a series of novel core‐modified and fused‐ring‐expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem‐crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine‐tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso‐phenyl rings, is also examined.     

A‐D‐A Type Small Molecules Based on Boron Dipyrromethene for Solution‐Processed Organic Solar Cells

The unique properties of boron dipyrromethene (BODIPY) dyes including facile synthesis, high absorption coefficients, and delocalized molecular orbitals as well as excellent photochemical and thermal stability, make them promising as materials for organic solar cells. Accordingly, in this study three A‐D ‐A structural small molecules of BDTT‐BODIPY, FL‐BODIPY, and TT‐BODIPY have been synthesized, in which two BODIPY acceptor units are symmetrically conjugated to 4,8‐bis(5‐(2‐ethylhexyl) thiophen‐2‐yl)benzo[1,2‐b:4,5‐b]dithiophene (BDTT), 9,9‐dioctyl‐9H‐fluorene (FL), and thieno[3,2‐b]thiophene (TT) donor cores, respectively. The manipulation of the structural parameters significantly improves the performances of the BHJ OSCs, which show power conversion efficiencies of 4.75 %, 1.51 %, and 1.67 % based on [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM) as the acceptor material and BDTT‐BODIPY, FL‐BODIPY, and TT‐BODIPY as the donor materials, respectively.     

Tailoring the photophysical and photovoltaic properties of boron-difluorodipyrromethene dimers

Five boron-difluorodipyrromethene(BODIPY) dimers have been designed and synthesized successfully via acid-catalysed condensation and Pd-catalysed cross-coupling reactions.The structural modification,including verifying the structures of the π-bridges,altering the positions the bridges link(meso-or β-positions),and regulating the molecular planarity,can modulate the photophysical properties and the aggregation behaviors of the five dimers efficiently.Solution-processed organic solar cells were fabricated to evaluate the photovoltaic properties of these molecules further either as acceptors or donors.When using as nonfullerene acceptor and blended with the polymer donor of PTB7,an opencircuit voltaic(V_(oc)) of 1.12 and 1.08 V was achieved from the thiophene and benzodithiophene bridged BODIPY dimers,respectively.This V_(oc) is among the top values achieved from the non-fullerene organic solar cells so far.     

Low Band Gap Donor–Acceptor Conjugated Systems Based on 3‐Alkoxy or 3‐Pyrrolidino‐4‐cyanothiophene and Benzothiadiazole Units

3‐Hexyloxy‐4‐cyanothiophene, 3‐pyrrolidil‐4‐cyanothiophene, and 3,4‐ethylenedioxythiophene (EDOT) units are used with benzothiadiazole as building blocks for the development of three new conjugated donor–acceptor–donor (DAD) derivatives. The DAD molecules have the central acceptor part, which is formed by combining electron‐withdrawing cyano groups and the benzothiadiazole moiety, in common. Theoretical calculations and UV/Vis and electrochemical data reveal the key role of the end‐capped donor to tune the electronic properties of the derivatives. A study of the electropolymerization process of the three derivatives shows the strong influence of the donor parts on both the reactivity of the precursors and the electronic properties of the resulting polymers. Derivatives end‐capped with pyrrolidinocyano thiophene or EDOT units lead to films of polymers presenting low band gaps of around 0.9–1.4 eV. Upon oxidation, the two polymers present different behavior. In the presence of the pyrrolidinocyano thiophene moieties, oxidation leads to a blueshift of the absorption bands, whereas with EDOT units a classical redshift, giving high absorption in the near‐IR region, is observed for the oxidized states.     

Effect of hexyl substituent groups on photophysical and electrochemical properties of the poly[(9,9‐Dioctyluorene)−2,7‐diyl‐alt‐(4,7‐bis (3‐Hexylthien‐5‐Yl)−2,1,3‐Benzothiadiazole)−2′,2″‐diyl]

The effect of the presence of hexyl group in thiophene on the photophysical and electrochemical properties of poly[(9,9‐dioctyluorene)?2,7‐diyl‐alt‐(4,7‐bis(3‐hexylthien‐5‐yl)?2,1,3‐benzothiadiazole)?2′,2″‐diyl] (F8TBT) is investigated. The copolymers present electron donor–acceptor architecture and are synthesized by Suzuki coupling reaction. The UV/Vis spectra show absorption maximum in the wavelength range of blue and orange, which are associated with different segments of the polymer backbone. Addition of hexyl substituent groups has a positive effect on the molar absorptivity and increases the emission and absorption intensities due to fluorene and thiophene‐benzothiadiazole‐thiophene (TBT) units, although an increment in the bandgap is observed. Cyclic voltammetry study of the polymer films reveal irreversible reduction and oxidation processes of the TBT units in the polymer chain and the HOMO and LUMO energy levels suggest ambipolar character for the polymers, while the electrochemical bandgaps are consistent with the absorbance measurements. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1975–1982     

可溶液加工的D-A-D型有机小分子的烷基链效应及光电性能

设计合成了3种可溶液加工的基于噻吩给体和2-吡喃-4-亚基丙二氰(PM)受体的新型Donor-Acceptor-Donor(D-A-D)型有机小分子TPT-N, TPT-S和TPT-D. 研究了噻吩给体单元上烷基链的数目对分子的溶解性、 光物理(吸收特性)、 热稳定和光电性能的影响. 结果表明, 随着烷基链的增加, 分子的溶解性增加, 成膜性能提高; 分子在溶液中的吸收光谱发生红移, 薄膜的吸收谱带变窄, 分子的最高占有分子轨道(HOMO)能级提高. 以D-A-D型有机小分子为给体, 富勒烯C₆₀衍生物-苯基-C₆₁-丁酸甲酯(PCBM)为受体制备了结构为ITO/PEDOT∶PSS/D-A-D∶PCBM/LiF/Al的体异质结太阳能电池. 研究结果表明, 基于单烷基链的TPT-S的太阳能电池具有相对较高的能量转换效率. 说明在D-A-D型有机小分子太阳能电池材料中, 烷基链的数目是决定材料性能及器件性能的重要因素之一.     

Effect of molecular mass on supramolecular organisation of poly(4,4'-dioctyl-2,2':5',2'-terthiophene)

The effect of the chain length on the type and extent of the 2D supramolecular organization in poly(4,4'-dioctyl-2,2':5',2'-terthiophene) (PDOTT) monomolecular layers deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM) and analyzed in terms of molecular modeling. The strictly monodispersed fractions of increasing molecular mass used in this study were obtained by chromatographic fractionation of the crude product of 4,4'-dioctyl-2,2':5',2'-terthiophene oxidative polymerization. STM investigations of PDOTT layers, deposited on HOPG from poly- and monodispersed fractions, show that polydispersity can be considered as a key factor seriously limiting supramolecular ordering. This is a consequence of significant differences in the type of supramolecular order observed for molecules of different chain length. It has been demonstrated that shorter molecules (consisting of 6 and 9 thiophene units) form well-defined two-dimensional islands, while the interactions between longer molecules (consisting of 12 and 15 thiophene units) become anisotropic. Consequently, for higher molecular mass fractions, the supramolecular organization is one-dimensional and consists of more or less separated rows of ordered macromolecules. In this case an increase of the chain length leads to amplification of the intermolecular interactions proceeding via interdigitation of the alkyl substituents of adjacent molecules. Polydispersed fractions show much less ordered organization because of the incompatibility of the supramolecular structures of molecules of different molecular masses. This finding is of crucial importance for the application of polythiophene derivatives in organic and molecular electronics since ordered supramolecular organization constitutes the condition sine qua non of good electrical transport properties.     

Fluoro‐protected carbazole main‐chain polymers as a new class of stable blue emitting polymers

The protection of the 3,6‐positions of 9‐alkyl‐9H‐carbazole repeat units with fluorine substituents in 2,7‐linked main‐chain polymers as well as in copolymers with triaryl amine repeat units affords blue emitting materials with enhanced electrolytic stability. The electronic conjugation of this new class of materials is more extended than that of the equivalent polymers where the 3,6‐positions are protected with methyl substitutions as a result of the smaller steric hindrance of their fluorine substituents. Attachment of fluorine‐protecting groups at the 3,6‐positions of carbazole repeat units in the homopolymers resulted in materials with relatively high ionization potentials (5.71 eV). However, introduction of triaryl amine comonomers as alternating repeat units provided carbazole/triaryl amine copolymers with a low ionization potential (5.25 eV), a very high quantum yield of fluorescence in solution (0.96), and narrow emission bands [full width at half maximum (FWHM) = 52 nm]. The preparation of this new class of materials together with a study of their electronic and photophysical properties is presented. Copyright © 2007 John Wiley & Sons, Ltd.     

Bipolar molecules with high triplet energies: synthesis, photophysical, and structural properties

This article sheds new light on the interplay of electronic and conformational effects in luminescent bipolar molecules. A series of carbazole/1,3,4-oxadiazole hybrid molecules is described in which the optoelectronic properties are systematically varied by substituent effects which tune the intramolecular torsion angles. The synthesis, photophysical properties, cyclic voltammetric data, X-ray crystal structures, and DFT calculations are presented. Excited state intramolecular charge transfer (ICT) is observed from the donor carbazole/2,7-dimethoxycarbazole to the acceptor phenyl/diphenyloxadiazole moieties. Introducing more bulky substituents onto the diphenyloxadiazole fragment systematically increases the singlet and triplet energy levels (E(S) and E(T)) and blue shifts the absorption and emission bands. The triplet excited state is located mostly on the oxadiazole unit. The introduction of 2,7-dimethoxy substituents onto the carbazole moiety lowers the value of E(S), although E(T) is unaffected, which means that the singlet-triplet gap is reduced (for 7bE(S) - E(T) = 0.61 eV). A strategy has been established for achieving unusually high triplet levels for bipolar molecules (E(T) = 2.64-2.78 eV at 14 K) while at the same time limiting the increase in the singlet energy.     

Synthesis,optical, and electrochemical properties of novel copolymers on the basis of benzothiadiazole and electron‐rich arene units

Novel alternating conjugated copolymers ( P1–P6 ) consisting of an electron‐deficient benzothiadiazole and a variety of electron‐rich thiophene‐arene‐thiophene units were synthesized by palladium‐catalyzed polycondensations (Stille and Suzuki reactions), aiming at processable materials with a reduced optical band gap. The structures of P1–P6 were confirmed by ¹H NMR and ¹³C NMR, and their molecular weights were determined by size exclusion chromatography. In the Suzuki polycondensation, the role of the catalyst [Pd(PPh₃)₄ and Pd(OAc)₂] on the resulting molecular weight was investigated. Pd(OAc)₂ enhances the molecular weight of the polymers for both thiophene and phenylene bis‐boronic esters as compared with Pd(PPh₃)₄. The optical properties of the polymers were examined in solution and the solid state. The polymers with n‐octyl substituents ( P1 , P4 , P5 , and P6 ) on the thiophene rings possessed less‐planar structures as a result of torsional steric hindrance, and their absorption spectra appeared blueshifted as compared with their unsubstituted analogues ( P2 and P3 ). The electrochemical properties of the polymers were studied using cyclic voltammetry. Although the alkyl substitution affects the oxidation potential, only marginal differences in the reduction potentials were observed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2360–2372, 2002     

Rational Design of Star-shaped Molecules with Benzene Core and Naphthalimide Derivatives End Groups as Organic Light-emitting Materials

A series of star-shaped molecules with benzene core and naphthalimides derivatives end groups have been designed to explore their optical,electronic,and charge transport properties as charge transport and/or luminescent materials for organic light-emitting diodes(OLEDs). The frontier molecular orbitals(FMOs) analysis has turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer(ICT). The calculated results show that the optical and electronic properties of star-shaped molecules are affected by the substituent groups in N-position of 1,8-naphthalimide ring. Our results suggest that star-shaped molecules with n-butyl(1),benzene(2),thiophene(3),thiophene S?,S?-dioxide(4),benzo[c][1,2,5]thiadiazole(5),and 2,7a-dihydrobenzo[d]thiazole(6) fragments are expected to be promising candidates for luminescent and electron transport materials for OLEDs. This study should be helpful in further theoretical investigations on such kind of systems and also to the experimental study for charge transport and/or luminescent materials for OLEDs.     

Design and Synthesis of Perpendicularly Connected Metal Porphyrin–Imide Dyads for Two‐Terminal Wired Single Molecular Diodes

Four different porphyrin–imide dyads bearing different central metals (zinc or rhodium) and different substituents on the porphyrin macrocycles (tert‐butyl or methoxy) were synthesized for single molecular diode measurements. The molecules were designed to separate the donor component (porphyrin) from the acceptor component (imide) by bonding in a perpendicular arrangement, thus enhancing the rectification properties. UV/Vis absorption spectra and density functional theory calculations showed that the design was successful and that the molecular orbitals of the dyads were the summation of the two components, with minimal interaction between them. The effect of the central metal was found to be significant, with the lowest energy absorption for the zinc dyads being attributed to the mixed state of charge transfer from porphyrin to imide and the Q band, whereas that of the rhodium dyads indicated insignificant charge‐transfer character.     

Fine Tuning the Performance of DSSCs by Variation of the π‐Spacers in Organic Dyes that Contain a 2,7‐Diaminofluorene Donor

Organic dyes that contain a 2,7‐diaminofluorene‐based donor, a cyanoacrylic‐acid acceptor, and various aromatic conjugation segments, which are composed of benzene, fluorene, carbazole, and thiophene units, as a π‐bridge have been synthesized and characterized by optical, electrochemical, and theoretical investigations. The trends in the absorption and electrochemical properties of these dyes are in accordance with the electron‐donating ability of the conjugating segment. Consequently, the dyes that contained a 2,7‐carbazole unit in the π‐spacer exhibited red‐shifted absorption and lower oxidation potentials than their corresponding fluorene‐ and phenylene‐bridged dyes. However, the enhanced power‐conversion efficiency that was exhibited by the fluorene‐bridged dyes in the DSSCs was attributed to their broader and intense absorption. Despite the longer‐wavelength absorption and reasonable optical density, carbazole‐bridged dyes exhibited lower power‐conversion efficiencies, which were ascribed to the poor alignment of the LUMO level in these dyes, thereby leading to the inhibition of electron injection into the TiO₂ conduction band.     

Highly Efficient Luminescent Solar Concentrators Based on Benzoheterodiazole Dyes with Large Stokes Shifts

Five extended π-conjugated systems with electron donor (D) and acceptor (A) moieties have been synthesized. Their basic D-A-D structural motif is a benzothiadiazole unit symmetrically equipped with two thiophene rings ( S2T ). Its variants include 1) the same molecular framework in which sulfur is replaced by selenium ( Se2T ), also with four thiophene units ( Se4T ) and 2) a D’-D-A-D system having a N-carbazole donor moiety at one end ( CS2T ) and a D’-D-A-D-A’ array with a further acceptor carbonyl unit at the other extremity ( CS2TCHO ). The goal is taking advantage of the intense luminescence and large Stokes shifts of the five molecules for use in luminescent solar concentrators (LSCs). All of them exhibit intense absorption spectra in the UV/Vis region down to 630 nm, which are fully rationalized by DFT. Emission properties have been studied in CH₂Cl₂ (298 and 77 K) as well as in PMMA and PDMS matrices, measuring photoluminescence quantum yields (up to 98 %) and other key optical parameters. The dye–PMMA systems show performances comparable to the present state-of-the-art, in terms of optical and external quantum efficiencies (OQE=47.6 % and EQE=31.3 %, respectively) and flux gain (F=10.3), with geometric gain close to 90. LSC devices have been fabricated and tested in which the five emitters are embedded in PDMS and their wave-guided VIS luminescence feeds crystalline silicon solar cells.     

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules

We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2‐thphCCM ( 1 ) and 3‐thphCCM ( 2 ), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2 . Theoretical calculations show the same trend. Self‐assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single‐molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.     

Thiophene-functionalized isoindigo dyes bearing electron donor substituents with absorptions approaching the near infrared region

A series of six new, highly soluble N,N'-dialkylated isoindigo derivatives bearing different electron donating thiophene units at the 6,6'-positions were synthesized by Stille cross-coupling reaction. The optical and electrochemical properties of these dyes were studied by UV-vis spectroscopy and cyclic voltammetry, revealing a good tunability of their electronic properties by peripheral substituents with amino groups leading to strong absorption reaching the NIR region. The DFT calculations of the frontier molecular orbitals of these dyes corroborate the observed substituent effect on absorption and redox properties.     

The Impact of a 1,2,3-Triazole Motif on the Photophysical Behavior of Non-K Tetrasubstituted Pyrene with a Substitution Pattern Providing the Long Axial Symmetry

1,3,6,8-Tetrasubstituted pyrene derivatives with two types of substituents (4-(2,2-dimethylpropyloxy)pyridine, 1-decyl-1,2,3-triazole, 1-benzyl-1,2,3-triazole, and pyrazole), substituted in such a way that provides the long axial symmetry, are prepared and characterized in the present study. To the best of our knowledge, the pyrene derivative containing the same heteroaryl motif (triazole) but substituted by two various alkyls, straight decyl and benzyl-based side chains (C), is reported for the first time. For comparison, compounds with one kind of triazole motif and substituted pyridine or pyrazole groups were prepared (A and B). The photophysical properties of all molecules were evaluated by thermogravimetric analysis (TGA) and UV-Vis spectroscopy (absorption and emission spectra, quantum yields, and fluorescence lifetimes). The obtained results were compared to analogues substituted at the 1,3,6,8 positions by one kind of substituent and also with all the 1,3,6,8-tetrasubstituted pyrenes reported in the literature substituted by two kinds of substituents with a substitution pattern that provides long axial symmetry. In addition, theoretical studies based on DFT and TD-DFT were performed that supported the interpretation of the experimental results. The photophysical properties of tetrasubstituted pyrene derivatives having triazole units at the 1,8-positions, respectively, and other identical substituents at the 3,6 positions show the dominance of triazole units in the pyrene framework; the dominance is even higher in the case of the substitution of 1,3,6,8 positions by triazoles, but containing two various alkyls.     

Direct arylation polymerization toward ultra‐low bandgap poly(thienoisoindigo‐alt‐diketopyrrolepyrrole) conjugated polymers: The effect of β‐protection on the polymerization and properties of the polymers

Direct arylation polymerization between derivatives of dibromodiketopyrrolopyrrole (DPP) and thienoisoindigo (TIIG) resulted in two π‐conjugated copolymers with average molecular weights up to 24.0 kDa and bandgaps as low as 0.8 eV. The structural analysis of the obtained two polymers revealed well‐defined alternating conjugation backbones without obvious structural defects. The introduction of hexyl‐group in the β‐position of thiophene rings in the DPP units not only reduces the bandgap of conjugated polymer compared to a similar polymer containing bare‐thiophene flanked DPP but also affects polymer morphology in thin films. P‐type charge‐transport characteristics were observed for two polymers in organic field‐effect transistors with comparable hole mobilities. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3205–3213