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Ferroelectric spin crossover (SCO) behavior is demonstrated to occur in the cobalt(II) complex, [Co(FPh‐terpy)2](BPh4)2⋅3ac (1⋅3 ac; FPh‐terpy=4′‐((3‐fluorophenyl)ethynyl)‐2,2′:6′,2′′‐terpyridine) and is dependent on the degree of 180° flip–flop motion of the ligand's polar fluorophenyl ring. Single crystal X‐ray structures at several temperatures confirmed the flip–flop motion of fluorobenzene ring and also gave evidence for the SCO behavior with the latter behavior also confirmed by magnetic susceptibility measurements. The molecular motion of the fluorobenzene ring was also revealed using solid‐state 19F NMR spectroscopy. Thus the SCO behavior is accompanied by the flip–flop motion of the fluorobenzene ring, leading to destabilization of the low spin cobalt(II) state; with the magnitude of rotation able to be controlled by an electric field. This first example of spin‐state conversion being dependent on the molecular motion of a ligand‐appended fluorobenzene ring in a SCO cobalt(II) compound provides new insight for the design of a new category of molecule‐based magnetoelectric materials. [ABSTRACT FROM AUTHOR]

• Density and speed of sound of (iodobenzene+ n -alkane) mixtures are measured at t = (288.15 K to 308.15 K) and p = 0.1 MPa. • Excess molar volume (V m E) and isentropic compressibility (κ S E) are calculated and correlated. (∂ V m E / ∂ T) p are also calculated. • The V m E results are compared with those (fluorobenzene, chlorobenzene or bromobenzene + n -alkane) mixtures. • The V m E variation with the n -alkane size is determined by the variation of the contribution from structural effects. • The Prigogine-Flory-Patterson model is applied and supports the conclusions from the analysis of experimental data. (Iodobenzene + n -alkane) liquid mixtures have been studied experimentally, in terms of densities (ρ) and speeds of sound (c), and theoretically, by the application of the Prigogine-Flory-Patterson (PFP) model. The n -alkanes considered are n -heptane, n -decane, n -dodecane, and n -tetradecane. ρ and c measurements have been performed at a pressure p = 0.1 MPa and in the temperature range T = (288.15 to 308.15) K. Excess molar volumes (V m E) and excess isentropic compressibilities (κ S E) have been calculated and correlated by Redlich-Kister polynomials. (∂ V m E / ∂ T) p curves at the same (p , T) conditions have been obtained from correlated V m E values. The mixtures are characterized by the following features: (i) V m E increases with the number of carbon atoms of the n -alkane (n), being negative for n = 7, small and S-shaped with positive and negative values for n = 10, and positive for n = 12 and n = 14; (ii) κ S E and (∂ V m E / ∂ T) p are negative, increase with n and are very close to zero for n = 14. From these experimental results and the knowledge of the excess molar enthalpies of mixtures containing fluorobenzene, chlorobenzene or bromobenzene with n -alkanes, we have inferred the presence of structural effects, especially important for n = 7 and less relevant for volumetric properties as n increases. The V m E obtained are compared with those of other (halogenated benzene + n -alkane) liquid mixtures existing in the literature, namely systems with fluorobenzene, chlorobenzene, and bromobenzene. From this comparison and the analysis of the isobaric thermal expansion coefficients of the pure compounds, it is inferred that the interactional effects on V m E do not vary appreciably with the length of the n -alkane, so the observed V m E variation is fundamentally determined by the corresponding variation of the contribution from structural effects. Moreover, the application of the PFP model supports this interpretation, providing free volume contributions to V m E that vary parallelly to V m E with the length of the n -alkane, and interactional contributions that rest approximately constant independently of the n -alkane size. [ABSTRACT FROM AUTHOR]

Azeotropes are boiling liquid mixtures which have identical vapor and liquid compositions. Known as polyazeotropy, azeotropic mixtures may exhibit more than one azeotrope at a given temperature or pressure. While the thermodynamic condition for azeotrope formation in vapor-liquid equilibrium is well established, thermodynamic modeling of mixtures exhibiting polyazeotropy remains challenging and prior modeling studies often failed to satisfactorily correlate the polyazeotropic behavior of associating systems. Based on the association NRTL model, this study presents successful correlation and analysis of double azeotrope formation for three diverse systems: strongly associating methanol + diethylamine binary, weakly associating ammonia + pentafluoroethane binary, and non-associating benzene + hexafluorobenzene binary systems. These systems exhibit polyazeotropic behavior as the temperature increases and approaches their Bancroft points. [ABSTRACT FROM AUTHOR]

A 1 : 1 mixture of aminomethylenehelicene (P)‐tetramer with C16 alkyl groups (P)‐1‐C16 and (M)‐pentamer (M)‐2 in fluorobenzene forms hetero‐double‐helices, and the processes of formation and dissociation exhibit thermal hysteresis on cooling and heating. When thermal triangle waves with repeated cooling and heating cycles are applied, unstable thermal hysteresis appears, which becomes a stable thermal hysteresis after sufficient numbers of cycles. The phenomenon of middle‐range stable thermal hysteresis is observed in this case. Properties of unstable and stable thermal hysteresis are examined under various thermal triangle waves. [ABSTRACT FROM AUTHOR]

A series of polyfluorobenzene, pyridine and aniline substituted berberine derivatives (3b-3h) were prepared via resin-supported Cu(II) catalyzed cross-coupling reactions of tetrahydroberberrubine with iodoarenes and subsequent I2 oxidation. The best catalyst, a polyethyleneimine functionalized polystyrene supported Cu2+ (PSAPA.Cu(II)), could be reused for at least 5 runs without significant loss of catalytic activity. Comparative studies on the morphology and porous structures of the materials suggested a catalyst with a moderate specific surface area and larger pore diameters was more active in catalyzing the cross-coupling reactions. [ABSTRACT FROM AUTHOR]

To study the role of the triiodide (I3)− anion in establishing various halogen bonding patterns, the trimethylphenylammonium iodide (NMe3PhI) salt was reacted with diiodine (I2) in the presence of a series of organoiodines, tetraiodoethylene (TIE), 1,2‐diiodo‐3,4,5,6‐tetrafluorobenzene (o‐F4DIB), 1,4‐diiodo‐2,3,5,6‐tetrafluorobenzene (p‐F4DIB), and 1,3,5‐trifluoro‐2,4,6‐triiodobenzene (1,3,5‐F3I3B) to form cocrystals of the organoiodines with the trimethylphenylammonium triiodide (NMe3PhI3) salt. Single‐crystal X‐ray crystallography revealed the (I3)− anion served as a halogen bond acceptor for the organoiodine donors, forming a variety of 1‐D, 2‐D, and 3‐D packing arrangements through I⋅⋅⋅I halogen bonding. Significant asymmetry was observed within the (I3)− anion. The melting points of the cocrystalline materials, as determined by simultaneous DSC/TGA, ranged from 43 °C to 119 °C and showed a strong dependence on the identity of the organoiodine incorporated into the crystal lattice. [ABSTRACT FROM AUTHOR]

A fluorobenzene based single electron transistor (SET) has been investigated for the detection of toxic gases viz. NH3, HCN, AsH3, and COCl2, within the framework of density functional theory (DFT) formalism based first-principles approach. Initially, the adsorption mechanism between the fluorobenzene quantum dot and the toxic gases (NH3, HCN, AsH3, and COCl2) has been analyzed in terms of adsorption energy, distance of adsorption, DOS profiles and the charge transfer analysis. Later, the exclusive property of charge stability diagram of SET has been utilized to provide the necessary electronic fingerprints for detection of toxic gases. The results suggest that the fluorobenzene SET can be a potential sensor for proposed toxic gases based on the wide operational temperature range and high detection ability as witnessed from the electronic fingerprints. [ABSTRACT FROM AUTHOR]

[Display omitted] The direction of the reaction between substituted perfluorobenzenes and thioacetic acid depends on the location of the substituents in perfluoroaromatic ring. Hexafluorobenzene reacts at positions 1 and 4, perfluoro- m -xylene reacts at positions 4 and 6, while perfluoroindane reacts at positions 5 and 6 to give the corresponding dithiols with para -, meta - and ortho -location of the thiol groups, respectively. Domino-reaction of perfluoroindane-5-thiol and its acetyl thioester affords hexadecafluoro-2,12-dithia-pentacyclo[11.7.0.03,11.05,9.015,19]icosa-1(13),3,5(9),10,14,19-hexaene [ABSTRACT FROM AUTHOR]

The direct carboxylation between the benzene C–H and CO2 is a long‐standing challenge in catalysis. Based on the known experimental process for the direct carboxylation of fluorobenzene, herein, a theoretical design of efficient carbene‐copper catalysts for the direct carboxylation of benzene was reported. It was found that the reaction included two steps: C–H bond breaking and CO2 insertion into Cu‐phenyl. C–H breaking is the rate‐determining step. To find out a more effective catalyst, totally, 16 carbene‐copper compounds with different electronic and steric structures were investigated. The energy barriers for the C–H bond breaking range from 104.2 to 153.7 kJ/mol. Two effective methods are proposed for improving the catalytic reactivity: reducing the electronically active substituent on carbene and introducing interaction to stabilize the transition state (TS). Based on these findings, adopting a well‐known (amino)(silyl)carbene modified by a –NH2 group gives the most effective catalyst for the direct carboxylation of benzene. Using –NH2 group can introduce two strong interactions (OOH···HNH2 and NNH2···Cu) during the formation of TS, which can greatly stabilize the structure of TS and dramatically reduce the energy barrier. The catalytic reactivity of the most effective carbene‐copper catalyst is comparable with the noble metal‐based ruthenium pincer carboxylate complexes. [ABSTRACT FROM AUTHOR]

Highly concentrated electrolytes (HCEs) significantly improve the stability of lithium metal anodes, but applications are often impeded by their limitation of density, viscosity, and cost. Here, fluorobenzene (FB), an economical hydrocarbon with low density and low viscosity, is demonstrated as a bifunctional cosolvent to obtain a novel FB diluted highly concentrated electrolyte (FB‐DHCE). First, the addition of FB suppresses the decomposition of dimethoxyethane (DME) on the Li metal by strengthening the interactions of DME and FSI− around Li+. Second, FB efficiently elevates the content of LiF in the solid electrolyte interphase (SEI) based on its electrochemical reduction reaction. The unique solvation and interfacial chemistry of FB‐DHCE enable dendrite‐free deposition of lithium with high Coulombic efficiency (up to 99.3%) and prolong cycling life (over 500 cycles at 1 mA cm−2). The performance of FB‐DHCE is further demonstrated in full cells under practical conditions, including ambient to low temperature (–20 °C), high areal capacity (7.6 mAh cm−2), high current density (3 mA cm−2), limited excess Li (20 µm Li), and lean electrolyte (3 g Ah−1). Employing FB as a cosolvent not only opens a novel pathway to stabilize Li metal anodes, but also could greatly advance the development of Li metal batteries. [ABSTRACT FROM AUTHOR]

Hexafluorobenzene undergoes 1,4‐selective thiol‐fluoride disubstitution and is an attractive disulfide crosslinking reagent for peptide cyclisation and stapling. Little attention has been directed toward understanding the scope of this reaction. Traditional reaction optimisation relies on a one‐variable‐at‐a‐time approach, which can exclude important combined effects of reaction variables. This study initially explored base and solvent effects to inform a subsequent two‐level factorial design approach to understand how to control the reactivity and product selectivity in a model reaction of hexafluorobenzene. We describe new conditions that selectively afford higher order substitution products for example, 1,2,4,5‐tetrasubstitution, making hexafluorobenzene a possible suitable scaffold for future branched or multicyclic peptide systems. Moreover, our new conditions provide an improved rapid (<1 minute) and selective peptide disulfide stapling and cyclisation approach under peptide‐compatible conditions. [ABSTRACT FROM AUTHOR]

The complexes of group 13 element trispentafluorophenyl derivatives E(C6F5)3 (E = B, Al, Ga, In) with diethyl ether of 1:1 composition have been synthesized and structurally characterized. All compounds are isostructural. Thermal stability studies reveal that at elevated temperatures all complexes decompose with pentafluorobenzene evolution. The geometries and thermodynamic characteristics for the dissociation reactions of the compounds have been computed using three DFT methods. The 1H NMR α‐proton chemical shifts for the coordinated ether in deuteriobenzene and in CD2Cl2 solutions correlate with gas phase dissociation enthalpies of the complexes. Potentially high Lewis acidity of B(C6F5)3 is hindered by the large pyramidalization energy of the acceptor moiety. [ABSTRACT FROM AUTHOR]

We present new evidence for the existence of a near threshold π* shape resonance as a common feature in the photoionization of each isomer of difluorobenzene. Experimentally, this is revealed by significant changes in the anisotropy of the photoelectron angular distributions (PADs) following the ionization of the optically aligned S1 state of these molecules at varying photon energies. Continuum multiple scattering Xα calculations reproduce this behaviour well, and allow the visualisation of the continuum shape resonances. The resonances are unusually narrow in energy (<1 eV), but nevertheless appear to extend right down to the ionization thresholds-exactly the low energy range typically accessed in laser-based resonance enhanced multiphoton ionization (REMPI) schemes. The anticipation of such pronounced energy dependence in the PADs and cross-sections sought for other molecules, and an ability to accurately predict such features, should be important for the reliable application and interpretation of experiments involving REMPI probing of those molecules. [ABSTRACT FROM AUTHOR]

Si(mply) rips it apart: C-F activation of fluorobenzene has been achieved using the extremely strong silyl Lewis acids [Et3Si(X)]+ (X=PhF or Et3SiH) and [(2,6-dixylyl-C6H 3)SiMe2] + paired with the anion CHB 11Cl11-. They abstract fluoride from unactivated fluorobenzene to give arylated products, consistent with phenyl-cation-like reactivity (see scheme). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

Si(mply) rips it apart: C-F activation of fluorobenzene has been achieved using the extremely strong silyl Lewis acids [Et3Si(X)]+ (X=PhF or Et3SiH) and [(2,6-dixylyl-C6H 3)SiMe2] + paired with the anion CHB 11Cl11-. They abstract fluoride from unactivated fluorobenzene to give arylated products, consistent with phenyl-cation-like reactivity (see scheme). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

Flexible and low‐power consuming integrated circuits are some of the basic requirements for smart wearable devices. High mobility solution‐processed organic field‐effect transistors (OFETs) have the potential to make a big impact in printed electronic circuits, but their overall performance is currently limited by unusually high threshold voltages (Vth). Herein, systematic optimization of donor–acceptor conjugated polymer, based on dithienothiophene (DTT) and thiophene‐flanked diketopyrrolopyrrole (DPP), namely, PDPPT–DTT, OFETs by application of self‐assembled monolayers (SAMs) at the semiconductor–dielectric, and semiconductor–metal interfaces is reported. The results clearly exhibit that simultaneous application of octyltrichlorosilane (OTS) as semiconductor–dielectric interface modifying layer and pentafluorobenzene thiol (PFBT) as semiconductor–metal interface modifying layer results in significantly lower Vth and subthreshold slope values from −14.07 V and 13.26 (V Dec−1) to +1.06 V and 7.11 (V Dec−1), respectively. This tailored approach is also beneficial in enhancing hole mobility values by an order of magnitude from 0.01 to 0.5 cm2 V−1 s−1 along with the possibility of switching from hole accumulation mode (Vth = −3.75 V) to depletion mode (Vth = +1.06 V) through device engineering. Simultaneous interface engineering reveals OFET electronic properties can be fine‐tuned for robust circuits and low power electronic applications. [ABSTRACT FROM AUTHOR]

Anion‐π catalysis functions by stabilizing anionic transition states on aromatic π surfaces, thus providing a new approach to molecular transformation. The delocalized nature of anion–π interactions suggests that they serve best in stabilizing long‐distance charge displacements. Aiming therefore for an anionic cascade reaction that is as charismatic as the steroid cyclization is for conventional cation‐π biocatalysis, reported here is the anion‐π‐catalyzed epoxide‐opening ether cyclizations of oligomers. Only on π‐acidic aromatic surfaces having a positive quadrupole moment, such as hexafluorobenzene to naphthalenediimides, do these polyether cascade cyclizations proceed with exceptionally high autocatalysis (rate enhancements kauto/kcat >104 m−1). This distinctive characteristic adds complexity to reaction mechanisms (Goldilocks‐type substrate concentration dependence, entropy‐centered substrate destabilization) and opens intriguing perspectives for future developments. [ABSTRACT FROM AUTHOR]

The geometric structures and vibration frequencies of para-chlorofluorobenzene (p-ClFPh) in the first excited state of neutral and ground state of cation were investigated by resonance-enhanced multiphoton ionization and slow electron velocity-map imaging. The infrared spectrum of S0 state and absorption spectrum for S1 ← S0 transition in p-ClFPh were also recorded. Based on the one-color resonant two-photon ionization spectrum and two-color resonant two-photon ionization spectrum, we obtained the adiabatic excited-state energy of p-ClFPh as 36302±4 cm−1. In the two-color resonant two-photon ionization slow electron velocity-map imagin spectra, the accurate adiabatic ionization potential of p-ClFPh was extrapolated as 72937±8 cm−1 via threshold ionization measurement. In addition, Franck-Condon simulation was performed to help us confidently ascertain the main vibrational modes in the S1 and D0 states. Furthermore, the mixing of vibrational modes between S0 → S1 and S1 → D0 has been analyzed. [ABSTRACT FROM AUTHOR]

Complexes formed by interaction of E(C6F5)3 (E = B, Al, Ga, In) with excess of acetonitrile (AN) were structurally characterized. Quantum chemical computations indicate that for Al(C6F5)3 and In(C6F5)3 the formation of a complex of 1:2 composition is more advantageous than for B(C6F5)3 and Ga(C6F5)3, in line with experimental observations. Formation of the solvate [Al(C6F5)3·2AN]·AN is in agreement with predicted thermodynamic instability of [Al(C6F5)3·3AN]. Tensimetry study of B(C6F5)3·CH3CN reveals its stability in the solid state up to 197 °C. With the temperature increase, the complex undergoes irreversible thermal decomposition with pentafluorobenzene formation. [ABSTRACT FROM AUTHOR]

Selective elimination of the fluorine element in organic fluorinated compounds under mild conditions is desired in order to resolve the environment and energy resource issues. Selective reductive defluorination of fluorine‐containing organic compounds in 2‐propanol‐water suspensions of metal‐loaded titanium(IV) oxide (TiO2) photocatalysts is described in this paper. The effects of different types of metal co‐catalysts, adsorption behavior of fluorobenzene (FB), stoichiometry, redox balance, scope, chemoselectivity and reaction temperature were examined. Photocatalytic defluorination of FB occurred over platinum‐loaded TiO2 at room temperature, and benzene and fluoride ion were produced with a high stoichiometry without degradation of the benzene structure, while hydrogen (H2) production occurred as a competitive electron‐consuming reaction. A slight elevation in the reaction temperature greatly accelerated defluorination and suppressed H2 evolution, resulting in FB defluorination free from H2 production at 333 K. Kinetic parameters of FB defluorination and H2 evolution were determined, and the results obtained are explained on the basis of these parameters. [ABSTRACT FROM AUTHOR]

Featured Application: Herein, we extend the application of low field nuclear magnetic resonance in the strong heteronuclear J-coupling regime to a series of fluorobenzene compounds. The results indicate that this spectral regime may be used for detailed spectroscopic analysis of small molecules. Chemical analysis via nuclear magnetic resonance (NMR) spectroscopy using permanent magnets, rather than superconducting magnets, is a rapidly developing field. Performing the NMR measurement in the strong heteronuclear J-coupling regime has shown considerable promise for the chemical analysis of small molecules. Typically, the condition for the strong heteronuclear J-coupling regime is satisfied at µT magnetic field strengths and enables high resolution J-coupled spectra (JCS) to be acquired. However, the JCS response to systematic chemical structural changes has largely not been investigated. In this report, we investigate the JCS of C6H6−xFx (x = 0, 1, 2, ..., 6) fluorobenzene compounds via simultaneous excitation and detection of 19F and 1H at 51.5 µT. The results demonstrate that JCS are quantitative, and the common NMR observables, including Larmor frequency, heteronuclear and homonuclear J-couplings, relative signs of the J-coupling, chemical shift, and relaxation, are all measurable and are differentiable between molecules at low magnetic fields. The results, corroborated by ab initio calculations, provide new insights into the impact of chemical structure and their corresponding spin systems on JCS. In several instances, the JCS provided more chemical information than traditional high field NMR, demonstrating that JCS can be used for robust chemical analysis. [ABSTRACT FROM AUTHOR]

Three new fluorinated bis(pyrazoles), namely: 1,4-bis(1H-pyrazol-4-ylethynyl)-2-fluorobenzene (H2BPEFB), 1,4-bis(1H-pyrazol-4-ylethynyl)-2,3-difluorobenzene (H2BPEF2B) and 1,4-bis(1H-pyrazol-4-ylethynyl)-tetrafluorobenzene (H2BPEF4B), have been synthesized taking advantage of Sonogashira coupling reactions, and characterized as per their crystal and molecular structure, spectroscopic and dielectric properties, and hydrophobicity. In the crystal structures, the three molecules, whose deviation from planarity increases on increasing the fluorination degree, interact by means of hydrogen bonds, forming 2D supramolecular layers. Notably, the absorption and fluorescence emission properties are only slightly affected by the fluorination degree in both the solid state and solution. Furthermore, the spectral line-shapes are weakly dependent on the environment when dissolved in a number of solvents of different polarity and hydrogen-bonding affinity. On the other hand, the dielectric constant monotonically increases on increasing the number of fluorine atoms. In silico molecular modeling with time-dependent density functional theory has offered a valuable means to rationalize the above mentioned behaviors and has shed some light on the ligand affinity towards representative gases – H2O and CO2 – and organic solvents – toluene. [ABSTRACT FROM AUTHOR]

The TBADT‐catalyzed C(sp3)–H functionalization of perfluorophenyl‐ and perfluoroalkyl‐substituted alkanes was studied to determine how the fluorous substituents affect site‐selectivity. Alkylation of alkyl‐substituted perfluorobenzene avoids α‐C–H bonds, unlike their alkylbenzene counterparts, allowing site‐selective functionalization of C–H bonds remote to the aromatic ring. Alkylation of alkanes having a perfluoroalkyl group also avoided α‐C–H bonds. Radical polar effects in the SH2 transition states could explain this avoidance of α‐C–H functionalization. [ABSTRACT FROM AUTHOR]

We demonstrate the performance of a dual frequency comb quantum cascade laser (QCL) spectrometer for the application of vibrational Stark spectroscopy. Measurements performed on fluorobenzene with the dual-comb spectrometer (DCS) were compared to results obtained using a conventional Fourier transform infrared (FT-IR) instrument in terms of spectral response, parameter estimation, and signal-to-noise ratio (S/N). The dual-comb spectrometer provided similar qualitative and quantitative data as the FT-IR setup in 250 times shorter acquisition time. For fluorobenzene, the DCS measurement resulted in a more precise estimation of the fluorobenzene Stark tuning rate ((0.81 ± 0.09) cm−1/(MV/cm)) than with the FT-IR system ((0.89 ± 0.15) cm−1/(MV/cm)). Both values are in accordance with the previously reported value of 0.84 cm−1/(MV/cm). We also point to an improvement of signal-to-noise ratio in the DCS configuration. Additional characteristics of the dual-comb spectrometer applicable to vibrational Stark spectroscopy and their scaling properties for future applications are discussed. [ABSTRACT FROM AUTHOR]

The aim of this work is to study the optical properties of the core-fluorinated azo-containing polyazomethines with 1,4-tetrafluorobenzene or 4,4′-octafluorobiphenylene dioxyphenylene units and aliphatic fragments in the chain. Due to the reorganization process at the nanometer-scale under UV/Vis irradiation, azo-containing polymers (APs) have attracted much attention as materials for biology, optoelectronics, nano-manipulation field, etc. Moreover, the introduction of azomethine group into these polymers enhances not only their optical properties but also expands their practical application. APs polymers have the useful combination of chemical and physical properties such as liquid crystalline states, high nonlinearity and an ability to form metal complexes. It was shown that the optical properties of such polymers could be improved by the inclusion of fluorine. Fluorinated polymers demonstrate high thermal stability and have low dielectric constant and dielectric losses. It should be noted that the presence of flexible moieties in a polymer backbone allows regulating the different properties (solubility, thermostability, optical and liquid crystalline properties) of the final materials. [ABSTRACT FROM AUTHOR]

The gas-phase copyrolysis of chlorotrifluoroethylene with buta-1,3-diene, penta-1,3-diene, or isoprene in a flow reactor at 440–480°C gave 4-chloro-4,5,5-trifluorocyclohex-1-enes. The latter treated with aqueous KOH under condition of phase-transfer catalysis were selectively converted into 1,2-difluorobenzene, 2,3-difluorotoluene, or 3,4-difluorotoluene. [ABSTRACT FROM AUTHOR]

The paper reports the reactions of the perfluorinated three‐mercury anticrown (o‐C6F4Hg)3 (1) with monohalogenobenzenes. It has been found that the interaction of 1 with fluorobenzene gives two 1:1 complexes 2 and 3, differing in their structures. Complex 2 forms in the crystal extended binary stacks wherein the molecules of 1 alternate with the halogenobenzene species, while complex 3 consists of the cofacial dimers formed from the corresponding monomeric units {[(o‐C6F4Hg)3](C6H5F)}. Each fluorobenzene molecule in both adducts is bonded to 1 by its phenyl ring through secondary π‐Hg–C interactions, whereas the fluorine atom is coordinated with one of the Hg sites of 1. Analogous types of bonding are realized in the chlorobenzene and bromobenzene complexes, {[(o‐C6F4Hg)3]2(C6H5X)4}, (X = Cl, Br), containing four halogenobenzene molecules per two molecules of 1. The complexes include two monomeric {[(o‐C6F4Hg)3](C6H5X)2} fragments connected with one another by two bridging η1 coordinated halogen atoms of the halogenobenzene ligands. The halogen atoms of two other halogenobenzene species are η3 coordinated each with the Hg centers of the neighboring molecule of 1. The reaction of iodobenzene with 1 affords a 3:1 complex, {[(o‐C6F4Hg)3](C6H5I)3}, which is unstable and readily transformed into the corresponding 1:1 adduct. Both compounds form in the crystal extended stacks wherein each sandwiched iodobenzene molecule is coordinated via the iodine atom with the adjacent molecule(s) of 1. [ABSTRACT FROM AUTHOR]

Sixteen intermolecular vibrational levels of the S0 state of the fluorobenzene-Ar van der Waals complex have been observed using dispersed fluorescence. The levels range up to ∼130 cm-1 in vibrational energy. The vibrational energies have been modelled using a complete set of harmonic and quartic anharmonic constants and a cubic anharmonic coupling between the stretch and long axis bend overtone that becomes near ubiquitous at higher energies. The constants predict the observed band positions with a root mean square deviation of 0.04 cm-1. The set of vibrational levels predicted by the constants, which includes unobserved bands, has been compared with the predictions of ab initio calculations, which include all vibrational levels up to 70-75 cm-1. There are small differences in energy, particularly above 60 cm-1, however, the main differences are in the assignments and are largely due to the limitations of assigning the ab initio wavefunctions to a simple stretch, bend, or combination when the states are mixed by the cubic anharmonic coupling. The availability of these experimental data presents an opportunity to extend ab initio calculations to higher vibrational energies to provide an assessment of the accuracy of the calculated potential surface away from the minimum. The intermolecular modes of the fluorobenzene-Ar2 trimer complex have also been investigated by dispersed fluorescence. The dominant structure is a pair of bands with a ∼35 cm-1 displacement from the origin band. Based on the set of vibrational modes calculated from the fluorobenzene-Ar frequencies, they are assigned to a Fermi resonance between the symmetric stretch and symmetric short axis bend overtone. The analysis of this resonance provides a measurement of the coupling strength between the stretch and short axis bend overtone in the dimer, an interaction that is not directly observed. The coupling matrix elements determined for the fluorobenzene-Ar stretch-long axis bend overtone and stretch-short axis bend overtone couplings are remarkably similar (3.8 cm-1 cf. 3.2 cm-1). Several weak features seen in the fluorobenzene-Ar2 spectrum have also been assigned. [ABSTRACT FROM AUTHOR]

The oxidative addition of a range of robust aryl C–F bonds to a single Al(I) center supported by a (NacNac)− bidentate ligand ((NacNac)− = [ArNC(Me)CHC(Me)NAr]− and Ar = 2,6–Pr2iC6H3) have been explored by density functional theory calculations. Our calculations demonstrate that the Al(I) center-mediated C–F insertion generally proceeds via the concerted mechanism that involve both the donation (nAl→σC-F*) and back-donation (σF(p)→πAl(p)*) interactions. In addition, the predicted free energy barriers for the C–F bond activation show good agreement with the experimental information available. Finally, the comparative studies show that B(I) is the most active among group III metals (B, Al, Ga), thus supplying a testable prediction for experiments.

The monitoring of Na+ ions distributed in the body has been indirectly calculated by the detection of Na+ ions in urine. We fabricated a two–dimensional (2D) Na+ ion sensor using a graphene ion–sensitive field–effect transistor (G–ISFET) and used fluorinated graphene as a reference electrode (FG–RE). We integrated G–ISFET and FG on a printed circuit board (PCB) designed in the form of a secure digital (SD) card to fabricate a disposable Na+ ion sensor. The sensitivity of the PCB tip to Na+ ions was determined to be −55.4 mV/dec. The sensor exhibited good linearity despite the presence of interfering ions in the buffer solution. We expanded the evaluation of the PCB tip to real human patient urine samples. The PCB tip exhibited a sensitivity of −0.36 mV/mM and linearly detected Na+ ions in human patient urine without any dilution process. We expect that G–ISFET with FG–RE can be used to realize a disposable Na+ ion sensor by serving as an alternative to Ag/AgCl reference electrodes.

Volumetric and acoustic properties of p-cymene with fluorobenzene, chlorobenzene and bromobenzene have been investigated using density, (ρ), and speed of sound, (U) measurements over the entire composition range at T= (303.15, 308.15 and 313.15) K. From the experimentally measured density, (ρ); Excess molar volumes, (V), infinite dilution partial molar volume, (, i) excess partial molar volume, (,) apparent molar volume, (V,m,ϕ, 1), infinite dilution apparent molar volume, (V,ϕ, 1) with empirical parameters, Sv, Bv and limiting apparent molar expansibility, (E) have been calculated. Deviation in speed of sound (U), deviation in isentropic compressibility, (ks), deviation in acoustic impedance, (z), infinite dilution partial molar isentropic compressibility, (,m, i), excess partial molar isentropic compressibility, (,i), apparent molar isentropic compressibility, (Ks,m,ϕ,i), infinite dilution apparent molar isentropic compressibility, (Km,ϕ,1) with empirical parameters Sk and Bk and intermolecular free length (Lf) have been calculated using experimentally measured speed of sound, (U). To derive fitting coefficients, (Ai) with standard deviation, (σ), excess properties were fitted to the Redlich-Kister type polynomial equation. Various theoretical speed of sound and average deviations have been calculated using well established equation like Nomoto, (Unmt) Ideal Mixing Rule, (Uimr) Junji, (Ujunji) and Jacobson's Free Length Theory, (Uflt). The variation of these properties with composition and temperature has been discussed in terms of molecular interaction on mixing and their interacting abilities have also been compared. [ABSTRACT FROM AUTHOR]

We review our development on beyond Born–Oppenheimer (BBO) theory and its implementation on various models and realistic molecular processes as carried out over the last 15 years. The theoretical formulation leading to the BBO equations are thoroughly discussed with ab initio calculations. We have employed first principle based BBO theory not only to formulate single surface extended Born–Oppenheimer equation to understand the nature of nonadiabatic effect but also to construct accurate diabatic potential energy surfaces (PESs) for important spectroscopic systems, namely, NO 2 radical, Na 3 and K 3 clusters, NO 3 radical, benzene and 1,3,5-trifluorobenzene radical cations ( C 6 H 6 + and C 6 H 3 F 3 + ) as well as triatomic reactive scattering systems like H + + H 2 and F + H 2 . The nonadiabatic phenomena like Jahn–Teller (JT), Renner–Teller, pseudo Jahn–Teller effects and the accidental conical intersections are the key players in dictating spectroscopic and reactive scattering profiles. The nature of diabatic coupling elements derived from ab initio data with BBO theory for molecular processes in Franck-Condon region has been analysed in the context of linearly and bilinearly coupled JT model Hamiltonian. The results obtained from quantum dynamical calculations on BBO based diabatic PESs of the above molecular systems are found to be in accord with available experimental outcomes. [ABSTRACT FROM AUTHOR]

In this study, novel palladium complexes containing N-heterocyclic carbene (NHC) ligands were synthesized and their structures characterized by ¹H NMR, 13C NMR and elemental analysis techniques. The catalytic activities of palladium-NHC complexes were tested in the direct arylation reactions of mono-fluorobenzenes with various aryl bromides. Palladium-NHC complexes showed the high catalytic activity for electron-donating and electron-drawing aryl bromides. [ABSTRACT FROM AUTHOR]

The coordination chemistry of phosphinines (phosphabenzenes) has been intensively investigated over the last decades, but metal complexes of halophosphinines and related halide‐substituted phosphacyclohexadienyls have remained scarce. Here, we describe the synthesis of a series of complexes [Cp*Fe(1‐F‐PC5Ph3H2)] (2‐F, Cp* = C5Me5), [Cp*Fe(1‐Cl‐PC5Ph3H2)] (2‐Cl), [Cp*Fe(PC5Ph3H2)]Br (2‐Br) and [Cp*Fe(PC5Ph3H2)]I (2‐I), which were obtained by reacting the previously reported 2,4,6‐triphenylphosphinine iron complex [K([18]crown‐6)(thf)2] [Cp*Fe(PC5Ph3H2)] (1) with electrophilic halogenating agents. To the best of our knowledge, 2‐F and 2‐Cl are the first π‐coordinated λ3‐halophosphacyclohexadienyl complexes with covalent P–X bonds (X = halogen). In the solid state 2‐Br and 2‐I show ionic structures with [Cp*Fe(PC5Ph3H2)]+ cations and separated X– anions. Anion exchange of I– in 2‐I for [BArF4]– {ArF = 3,5‐(CF3)2C6H3} affords [Cp*Fe(PC5Ph3H2)][BArF4] (2‐[BArF4]), which also displays an ionic structure. These new complexes were further characterized by solid‐state and solution 31P NMR spectroscopy, UV/Vis spectroscopy, elemental analyses, electrical conductivity measurements in solution, and DFT calculations. The resulting data indicate that 2‐F retains its covalent P–F bond in THF, fluorobenzene, and acetonitrile solution, while the remaining 2‐X complexes containing heavier halogen atoms (X = Cl, Br, and I) apparently form ion pairs in such solvents. The full set of halide‐substituted phosphacyclohexadienyl iron complexes was synthesized. A thorough comparison of their molecular structures, spectroscopic and computational data indicates the presence of polarized phosphorus–halogen bonds. Depending on the halogen atom, the P–X bonds show a distinct tendency to dissociate in the solid state and in solution. [ABSTRACT FROM AUTHOR]

Abstract Practical preparations of dichloromethyl alkyl ethers are described, based on the reaction of alkyl formates with oxalyl chloride in the presence of N -methylformanilide. The method involves a simple procedure that does not require the use of harmful reagents. Dichloromethyl propyl and dichloromethyl butyl ethers represent secure synthetic equivalents to dichloromethyl methyl ether. Formylations of both electron-deficient and electron-rich aromatics with these dichloromethyl alkyl ethers in the presence of AlCl 3 , FeCl 3 , or TiCl 4 have been systematically investigated. A plausible mechanism of formylation is discussed. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]

Iodopentafluorobenzene (IPFB or PhFI) was co-crystallized with tetra(n-butyl)ammonium tetraiodo-μ,μ′-diiododiplatinate(ii), [n-Bu4N]2[Pt2(μ-I2)I4] (1), to give the adduct 1·2IPFB. The XRD experiment revealed that 1·2IPFB displays previously unreported C…I–Pt anion–π interactions formed along with the expected PhF–I…I–PtII halogen bond (XB); these two interactions join two complexes and two IPFBs in a heterotetrameric cluster. Processing of the available CSD data revealed only one structure (CSD code: IKIYAE) with a heterotetrameric cluster bearing simultaneous two PhF–I…X (X = I–PtIV, N) XBs and C…I lp(I)–π contacts between the two IPFBs. Results of the DFT calculations (M06/DZP-DKH level of theory) followed by the topological analysis of the electron density distribution within the framework of Bader's approach (QTAIM) for both 1·2IPFB and IKIYAE confirmed the availability of these (anion/lp)–π weak interactions. The estimated energies of the observed (anion/lp)–π and XBs contacts are in the 0.9–1.3 kcal mol−1 and 1.3–5.3 kcal mol−1 ranges, respectively. π-Hole donor ability of IPFB was additionally confirmed by theoretical calculations of the molecular surface electrostatic potential for the optimized equilibrium structure of IPFB. [ABSTRACT FROM AUTHOR]

Bromo- and iodo-pentafluorobenzene (C6F5X, X = Br, I) exhibit intriguing σ- and π-hole characters, which are able to accept electrons, whereas furan (C4H4O) and thiophene (C4H4S) are able to donate electrons because of their electron-rich atoms and groups (i.e., the O atom and π-ring in C4H4O and the π-ring in C4H4S). Theoretical investigations of intermolecular interactions in these systems (i.e., C4H4O and C6F5Br, C4H4S and C6F5Br, C4H4O and C6F5I, and C4H4S and C6F5I) have been carried out at the M06-2X/aug-cc-pVDZ and wB97-XD/aug-cc-pVDZ levels with and without the counterpoise method, together with single-point calculations at the CCSD(T)/aug-cc-pVDZ level. For the system of C4H4O and C6F5X (X = Br, I), five different dimers, namely, I–V and I′–V′, which are connected by σ-hole…n, σ-hole…π and π-hole…π bonds, were found. Moreover, for the system of C4H4S and C6F5Br, four different dimers, namely, VI–IX, which are connected by σ-hole…π and π-hole…π bonds, were found. However, five dimers, namely, VI′–X′, were found for the system of C4H4S and C6F5I, which are connected by σ-hole…π, π-hole…π and σ-hole…n bonds. The driving forces for the formation of these dimers were revealed by EDA analyses. NCI, QTAIM and NBO analyses were employed to prove the existence of intermolecular interactions in these dimers and to elucidate their nature. The results presented here will be insightful for the study of other intermolecular systems that involve σ- and π-holes. [ABSTRACT FROM AUTHOR]

• 1-Tetrafluorophenyl-perfluoro-1-phenylpropanes were synthesized. • 1-Tetrafluoropheny-l-(pentafluorophenyl)prop-1-yl cations were generated. • Polyfluorinated diphenylpropanes undergo cyclization into polyfluoro-9-ethylfluorenes. • A convenient method for the synthesis of perfluoro-9-ethylfluorene has been developed. The interaction of perfluoropropylbenzene with 1,2,3,4-tetrafluorobenzene or 1,2,4,5-tetrafluorobenzene in an SbF 5 medium at r.t. yields corresponding 1-(tetrafluorophenyl)perfluoro-1-phenylpropanes, which undergo cyclization into perfluoro-9-ethylfluorene or 1,2,3,4,5,7,8,9-octafluoro-9-(pentafluoroethyl)fluorene along with 1,2,3,4-tetrahydro-9 H -fluorenes under the reaction conditions. The reaction of perfluoropropylbenzene with 1,2,3,5-tetrafluorobenzene under the same conditions leads to the formation of 1-(2,3,4,6-tetrafluorophenyl)perfluoro-1-phenylpropane, which does not give cyclization products at 50–55 °C. [Display omitted] [ABSTRACT FROM AUTHOR]

Recently, temporary anion states of fluorine substituted benzenes have been probed via photodetachment experiments on oxygen-fluorobenzene anion complexes [O 2 ⋅ C 6 H 6 − n F n ] − , n = 0 ... 6. Here, we complement these experiments with a computational characterization. For the ground electronic states, two isomers are identified: The first isomer class shows non-conventional hydrogen bonds, while the second shows carbon-oxygen contacts. For both isomer classes, the electron affinity of the complex is significantly higher than that of either moiety, and the electron affinity increase upon complex formation is studied in detail. Both isomer classes show strong O 2 − − C 6 H 6 − n F n interactions, and the extent of charge donation from O 2 − to the organic moiety is characterized. Moreover, we characterize charge-transfer excited states of [O 2 ⋅ C 6 H 6 − n F n ] − anion complexes corresponding to neutral O 2 bound to C 6 H 6 − n F n −. The charge transfer complexes form doublets and quartets, and here we focus on the minimal energy structure of the quartet state and characterize the doublet at the same geometry. [Display omitted] • Photodetachment probes charge-transfer excitations in anion-molecule complexes. • O 2 − and flurorinated benzenes form strongly bound anion-molecule complexes. • Possible binding motifs: non-conventional hydrogen bonds and C O contacts. • Hydrogen bonded complexes show little anion to molecule charge donation. • C O bonded complexes show substantial anion to molecule charge donation. [ABSTRACT FROM AUTHOR]

Electrochromic devices based on high-performance polymer materials with exceptional optical contrast, superior cycling stability, and large coloration efficiency are critical for the advancement of electrochromics, and have the potential to innovate a broad range of applications, including flexible displays and wearable electronics. Here, we design and synthesize three precursors of fluorobenzene-3-methylthiophene D-A-D type polymers through one-step Stille coupling, and then prepare the corresponding polymer films with good electrochemical and electrochromic properties via low-potential electropolymerization at 0.52 V vs Ag/AgCl. Interestingly, such polymers exhibit overall high electrochromic performances during the electrochemical reaction with inversible color changes between yellow and dark blue, including high optical contrast (83% at 1050 nm), fast response time (1.4 s / 0.8 s), and long-term stability (< 2% reduction after 250 cycles). As-fabricated electrochromic devices display excellent cycling stability (< 3% optical contrast degradation after 1,000 cycles) at a low drive voltage (0.8 V). Due to these excellent electrochromic properties, d -A-D type polymers based on fluorobenzene-3-methylthiophene can be further developed for practical applications such as near-infrared camouflage and E-displays. [Display omitted] [ABSTRACT FROM AUTHOR]

Chemical analysis via nuclear magnetic resonance (NMR) spectroscopy using permanent magnets, rather than superconducting magnets, is a rapidly developing field. Performing the NMR measurement in the strong heteronuclear J-coupling regime has shown considerable promise for the chemical analysis of small molecules. Typically, the condition for the strong heteronuclear J-coupling regime is satisfied at µT magnetic field strengths and enables high resolution J-coupled spectra (JCS) to be acquired. However, the JCS response to systematic chemical structural changes has largely not been investigated. In this report, we investigate the JCS of C6H6−xFx (x = 0, 1, 2, …, 6) fluorobenzene compounds via simultaneous excitation and detection of 19F and 1H at 51.5 µT. The results demonstrate that JCS are quantitative, and the common NMR observables, including Larmor frequency, heteronuclear and homonuclear J-couplings, relative signs of the J-coupling, chemical shift, and relaxation, are all measurable and are differentiable between molecules at low magnetic fields. The results, corroborated by ab initio calculations, provide new insights into the impact of chemical structure and their corresponding spin systems on JCS. In several instances, the JCS provided more chemical information than traditional high field NMR, demonstrating that JCS can be used for robust chemical analysis.

1-Fluoro-2,5-dimethoxy-4-nitrobenzene was synthesized in 90% yield by the reaction of commercial 2-fluoro-1,4-dimethoxybenzene with nitric acid. The structure was confirmed by X-ray crystallography. The new title compound was characterized by 1H and 13C-NMR, elemental analysis, EI-MS and FT-IR.

The isolation and solid-state characterisation of complexes featuring partially coordinated benzene, fluorobenzene and all three isomers of difluorobenzene are described. Supported by a DFT analysis, this well-defined homologous series demonstrates the preference for η2-coordination of fluoroarenes via the HC＝CH sites adjacent to a fluorine substituent. [ABSTRACT FROM AUTHOR]

Highlights • Sertraline and paroxetine were submitted to thermal, and hot stage microscopy analysis. • Paroxetine presented concomitant dehydration and melting followed by crystallization. • It decomposed in three mass loss steps releasing HCl, piperidine, fluorobenzene and CO 2. • Sertraline undergoes sublimation or solid transformation depending on the heating rate. • Decomposition occurred in two steps releasing methylamine, tetraline, dichlorobenzene and HCl. Abstract Antidepressants paroxetine and sertraline both as their hydrochlorides were studied regarding thermal behavior by TG/DTG-DTA, DSC, hot-stage microscopy, X-ray diffraction and coupled TG-FTIR. Paroxetine presented a single mass loss step after dehydration, in nitrogen. However, DTA curve revealed that such degradation actually occurs in three steps, in which HCl, piperidine, fluorobenzene and CO 2 are released. In air decomposition took place in a similar way. DSC showed endothermic peaks related to melting and dehydration of paroxetine. During evolved gases analysis it was possible to observe overlapped signals related to HCl and piperidine absorption. Sertraline, on its turn, presented sublimation when slowly heated or alternatively a solid transition from Form II to Form III at c.a. 199 °C followed by two mass losses when heated at higher heating rates. In the first degradation step methylamine is released. The second step is related to the loss of tetraline, dichlorobenzene and HCl, as revealed by TG-FTIR. Based on these data, thermal decomposition mechanisms were proposed for both drugs. [ABSTRACT FROM AUTHOR]

Three π-conjugated small molecules (SMs) with D(π-A-Ar) 2 molecular frameworks are designed and synthesized as the donor materials in organic solar cells (OSCs). Containing tetrafluorobenzene (TFB) as central donor (D) core, thiophene as π-bridge, 2-octylthiophene (T) as terminal (Ar) unit, as well as the different arm of acceptor (A) units, pyridine-diketopyrrolopyrrole (PyDPP), thiophene-diketopyrrolopyrrole (TDPP) and isoindigo (IID), namely DTTFB(PyDPP-T) 2 , DTTFB(TDPP-T) 2 and DTTFB(IID-T) 2 , respectively. The impacts of the different acceptor arms combined with the TFB core on the optical absorption, electrochemical property, hole mobility, film morphology, and solar cell performance were studied thoroughly. As a result, these SMs presented various light absorption properties, electrochemical performances, and hole mobilities, which are helpful to the optimization of short-circuit current ( J sc ), open-circuit voltage ( V oc ) and fill factor (FF) properties, respectively. Especially, the DTTFB(TDPP-T) 2 showed a relatively lower optical band gap of 1.53 eV, and also showed the best coplanarity among the three SMs, which help it to get a higher J sc of 12.44 mA cm −2 and a higher FF of 59.50%, and resulting in obtaining a best power conversion efficiency (PCE) of 5.15% in the DTTFB(TDPP-T) 2 /PC 71 BM-based cells, which is about 2.8 and 1.6 times higher than that of DTTFB(PyDPP-T) 2 /PC 71 BM and DTTFB(IID-T) 2 /PC 71 BM based cells, respectively. Obviously, introducing different acceptor units as arms onto the D(π-A-Ar) type SMs could be a promising strategy for designing high-performance TFB-based linear molecular donor materials. [ABSTRACT FROM AUTHOR]

An efficient chemoenzymatic route was developed for synthesis of ( S )-α-amino-4-fluorobenzeneacetic acid, a valuable chiral intermediate of Aprepitant, using immobilized penicillin amidase catalyzed kinetic resolution of racemic N -phenylacetyl-4-fluorophenylglycine. The optimum temperature, pH and agitation rate of the reaction were determined to be 40 °C, 9.5 and 300 rpm, respectively. Kinetic resolution of 80 g L −1 N -phenylacetyl-4-fluorophenylglycine by immobilized amidase 20 g L −1 resulted in 49.9% conversion and >99.9% e.e. within 3 h. The unreacted N -phenylacetyl-4-fluorophenylglycine can be easily racemized and then recycled as substrate. The production of ( S )-α-amino-4-fluorobenzeneacetic acid was further amplified in 1 L reaction system, affording excellent conversion (49.9%) and enantioselectivity (99.9%). This chemoenzymatic approach was demonstrated to be promising for industrial production of ( S) -α-amino-4-fluorobenzeneacetic acid. [ABSTRACT FROM AUTHOR]

In this work, two wide-bandgap polymers PBDTBT-1FB and PBDTBT-2FB were designed and synthesized with fluorobenzene (1FB) and difluorobenzene (2FB), respectively, which were inserted between the benzodithiophene (BDT) and benzothiadiazole units (BT) in polymer backbone. Functionalization of the phenylene unit with fluorine atom has a significantly effect on the energy levels and charge transportation properties of the polymers. Both PBDTBT-1FB and PBDTBT-2FB exhibited wide-bandgaps of ∼1.98 eV with deeper-lying HOMO levels. PBDTBT-2FB containing 2FB showed better hole transportation abilities than PBDTBT-1FB due to its good film quality. As a result, polymer PBDTBT-1FB containing 1FB has reached power conversion efficiency (PCE) of 2.16%, with open circuit voltage ( V oc ) of 0.95 V in optimized devices. The photovoltaic performance of PBDTBT-2FB was improved by increasing its V oc up to 1.0 V, resulting in a PCE of 3.34%. The wide-bandgap polymers containing fluorinated phenylene units result in the simultaneous promotion of V oc . [ABSTRACT FROM AUTHOR]