A Tetrathiafulvalene‐Based Electroactive Covalent Organic Framework

Two‐dimensional covalent organic frameworks (2D COFs) provide a unique platform for the molecular design of electronic and optoelectronic materials. Here, the synthesis and characterization of an electroactive COF containing the well‐known tetrathiafulvalene (TTF) unit is reported. The TTF‐COF crystallizes into 2D sheets with an eclipsed AA stacking motif, and shows high thermal stability and permanent porosity. The presence of TTF units endows the TTF‐COF with electron‐donating ability, which is characterized by cyclic voltammetry. In addition, the open frameworks of TTF‐COF are amenable to doping with electron acceptors (e.g., iodine), and the conductivity of TTF‐COF bulk samples can be improved by doping. Our results open up a reliable route for the preparation of well‐ordered conjugated TTF polymers, which hold great potential for applications in fields from molecular electronics to energy storage.     

Stable π-π dependent electron conduction band of TPP[M(Pc)L2]2 molecular conductors (TPP = tetraphenylphosphonium; M = Co, Fe; Pc = phthalocyaninato; L = CN, Cl, Br)

The partially-oxidized TPP[M(Pc)L(2)](2) molecular conductors exhibit variable electronic and magnetic transport bulk materials properties due to central metal and axial ligand molecular modifications. The controllable electrical conductivity and giant negative magnetoresistance can be mainly attributable to the varying ligand field energy and physical bulkiness of the axial ligands which cause modulation in the intra-molecular π-d (Pc-M) and inter-molecular π-π (Pc-Pc) interactions in the TPP[M(Pc)L(2)](2) system, respectively. Characterization of the electronic conduction band utilizing one-dimensional (1-D) tight-binding approximation from infrared reflectance and thermoelectric power profile reveal consistent band widths of 0.43 eV-0.62 eV for the Co series (L = Br < Cl < CN) and 0.44-0.56 eV for the Fe series (L = Br < Cl < CN). The fixed band width suggests that stable electron conduction bands (transport pathway) can be constructed which can withstand the molecular π-d interaction modifications that severely alter the bulk electronic and magnetic materials properties of the TPP[M(Pc)L(2)](2) molecular conductors.     

Conducting Polymers: Partially Oxidized Bridge-Stacked Metallophthalocyanines

The synthesis and characterization of a novel class of polymeric phthalocyanines (Pc), (PcMX)_n (M-Al, Ga, Cr; X?F and M-Si, Ge, Sn; X?0) of exceptional thermal stability are summarized. These materials possess a linear MX backbone surrounded by a sheath of cofacial M-centered Pc rings.

(PcAlF)_n and (PcGaF)_n are sublimable (10^?3mmHg,540°C and 430°C, respectively) allowing for thin film formation. Iodine-doping leading to compositions (PcMXI_y)_n with y ranging from 0.06 to 5.5 is reported. Thermogravimetric analysis has proven useful for iodine analyses and has revealed that the order of thermal stability with regard to loss of iodine is (PcCrFI_y)_n < (PcGaFI_y)_n< (PcAlFI_y)_n

< (PcSioI_y)_n. Raman spectra point to I₃-and I₅-as the principle polyiodide species, though their relative proportions vary depending on M and doping level. Increases in the electrical conductivity by as much as 10⁹ with maximum conductivities in the range of 0.01–1 ohm^?1cm^?1 result from iodine doping. Conduction appears to be thermally activated (77–300K) with an apparent activation energy of 0.04eV. It is likely that electron transport is primarily ligand based and is metal-like in character.     

Oxygenation of conducting polymers facilitated by structure-breaking anions

Conducting polymers are an interesting class of materials that can be tuned to have a range of properties through counterion doping. For most conducting polymers, the insertion of anions (the doping process) leads to the formation of carbocations (positive charge carriers) along the conjugated polymer backbone. In this research, we report on a scenario that arises where certain (commonly used) anions in water induce oxygenation of the conducting polymers heteroatom. This is in contrast to the widely reported doping process, and the recently reported hydrolysis of conducting polymers. We observe that the transition between these different conducting polymer-interactions/reactions is well described by the concept of structure-making and structure-breaking anions. Poly(3,4-propylenedioxy thiophene dimethyl) (PProDOT-Me₂), polypyrrole (PPy), and poly(3,4-ethylenedioxy thiophene) (PEDOT) thin films are exposed to a range of anions in water. Both PProDOT-Me₂ and PPy are susceptible to oxygenation, while in contrast PEDOT is doped, when exposed to structure-breaking anions. All the polymers show hydrolysis for structure-making anions. The knowledge of the interaction and/or reaction of conducting polymers with anions in water is not only critical to their application in devices for aqueous environments (i.e., sensing), but also for their processing and fabrication using water.     

NONCONJUGATED CONDUCTIVE POLYMERS

Conjugation is not a prerequisite for a polymer to be conductive. A polymer must have at least one double bond in the repeat to become conductive. Interaction with a dopant (e.g., electron acceptor) causes transfer of an electron from the double bond to the dopant creating a hole at the double bond site. Electrical conduction occurs via intersite hopping of holes. Various spectroscopic methods (FTIR, optical absorption, solid-state ¹³C NMR, etc.) along with electrical measurements have been used to elucidate the mechanism of conduction in specific nonconjugated conductive polymers. Examples of these polymers include 1,4-polyisoprene which has one double bond and three single bonds in the repeat. The conductivity of polyisoprene increases 100 billion times upon doping with iodine to a maximum value of 10 S/m. Polyisoprene (natural rubber) is used nonconjugated conductive polymers have a wide range of applications in antistatics, various sensors and optoelectronics.     

Sulfurization of polymers. 4. Poly(4,5,6,7-tetrathiono-4,5,6,7-tetrahydrobenzothiophene-2,3-diyl) and related structures based on polystyrene and elemental sulfur

Polystyrene was exhaustively sulfurized with elemental sulfur at 190--370 °C to liberate hydrogen sulfide and to form black lustrous powders (the sulfur content was up to 67%) possessing conductivity (10^–7--10^–6 S cm^–1 upon doping with I₂), paramagnetic properties ((3.4--13)·10¹⁹ sp g^–1, g = 2.0040--2.0046, H = 0.36--0.47 mT), and redox properties. The use of these polymers as active cathode materials in lithium batteries allows their repeated cycling at a specific discharge capacity of up to 330 mA h g^–1. The data of elemental analysis and differential scanning calorimetry, the IR and ESR spectra, the conductivities, and the character of electrochemical activity of the polymers synthesized are consistent with poly(4,5,6,7-tetrathiono-4,5,6,7-tetrahydrobenzothiophene-2,3-diyl) and related structures.     

First‐Principles Study on Doping of SnSe2 Monolayers

Doping is a vitally important technique that can be used to modulate the properties of two‐dimensional materials. In this work, by using first‐principles density functional calculations, we investigated the electrical properties of SnSe₂ monolayers by p‐type/n‐type and isoelectronic doping. Substitution at Sn/Se sites was found to be easy if the monolayer was grown under Sn‐/Se‐poor conditions. Substitutions at Sn sites with metallic atoms (e.g. Ga, Ge, In, Bi, Sb, Pb) resulted in positive substitution energies, which indicated that they were not effective doping candidates. For substitutions at Se sites with nonmetallic atoms, no promising candidates were found for p‐type doping (e.g., N, P, As). Among these, N and As showed positive substitution energies. Although P had a negative substitution energy under Sn‐rich conditions, it introduced trap states within the band gap. For n‐type doping (e.g., F, Cl, Br), all the calculated substitution energies were negative under both Sn‐ and Se‐rich conditions. Br was proven to be a promising candidate, because the impurity introduced a shallow donor level. Finally, for isoelectronic doping (e.g., O, S, Te), the intrinsic semiconducting features of the SnSe₂ monolayer did not change, and the contribution from the impurity to the states near the band edge increased with the atomic number.     

Potassium magnesium and potassium cobalt molybdates: Synthesis and ion conductivity

Potassium magnesium and potassium cobalt molybdates of composition K₂M ₂ ^II (MoO₄)₃ (M = Mg, Co) and the products of their heterovalent doping by scandium(III) and vanadium(V) ions have been studied by impedance spectroscopy, powder X-ray diffraction, and electron microscopy. The compounds have high ion conductivity. Partial heterovalent substitutions of scandium for magnesium or vanadium for molybdenum additionally increases ion conductivity. The high conductivity of potassium magnesium and potassium cobalt molybdates allows us to consider them as promising solid electrolytes with potassium conductivity.     

New π‐Conjugated Polymers Containing 1,3,5‐Triazine Units in the Main Chain: Synthesis and Optical and Electrochemical Properties of the Polymers

Summary: Three new soluble π‐conjugated polymers containing 1,3,5‐triazine units in the main chain, Pa–Pc, were synthesized. The polymers showed optical properties in solution that were mainly dependant on the properties of the substituting R groups, on the triazine ring. Hence, Pa and Pb (R = H and  OCH₃, respectively) showed blue photoluminescent (PL) emission with high quantum yields (QY) even in polar solvents, whereas Pc (R = N,N‐dimethylamino) gave green‐blue PL emission with very low QY. The PL spectra of the polymers in solution were concentration and polarity dependent, which suggested the formation of an exciplex.

The three new soluble π‐conjugated polymers containing 1,3,5‐triazine units in the main chain synthesized here.     

Pre-Polymerization Enables Controllable Synthesis of Nanosheet-Based Porphyrin Polymers towards High-Performance Li-Ion Batteries

The precise regulation of nucleation growth and assembly of polymers is still an intriguing goal but an enormous challenge. In this study, we proposed a pre-polymerization strategy to regulate the assembly and growth of polymers by facilely controlling the concentration of polymerization initiator, and thus obtained two kinds of different nanosheet-based porphyrin polymer materials using tetrakis-5,10,15,20-(4-aminophenyl) porphyrin (TAPP) as the precursor. Notably, due to the π–π stacking and doping of TAPP during the preparation process, the obtained PTAPP-nanocube material exhibits a high intrinsic bulk conductivity reaching 1.49×10⁻⁴ S m⁻¹. Profiting from the large π-conjugated structure of porphyrin units, closely stacked layer structure and excellent conductivity, the resultant porphyrin polymers, as electrode materials for lithium ion batteries, deliver high specific capacity (≈650 mAh g⁻¹ at the current density of 100 mA g⁻¹), excellent rate performance and long-cycle stability, which are among the best reports of porphyrin polymer-based electrode materials for lithium-ion batteries, to the best of our knowledge. Therefore, such a pre-polymerization approach would provide a new insight for the controllable synthesis of polymers towards custom-made architecture and function.     

Charge transport in stacking metal and metal‐free phthalocyanine iodides. Effects of packing,dopants, external electric field,central metals,core modification,and substitutions

The charge‐transport properties of the one‐dimensional stacking metal phthalocyanine iodides (M(Pc)I, M = Fe, Co, Ni, Cu) and metal‐free phthalocyanine iodide (H₂(Pc)I) have been theoretically investigated. On the basis of the tight‐binding approximation and two‐state theory, both the site‐energy corrected energy splitting in dimer and Fock‐matrix‐based methods are used to calculate the transfer integral. The intermolecular motions, including interplanar translation, rotation, slip, and tilt, exert remarkable impacts on the transfer integral. The order/disorder of the dopant stack and the long‐range electrostatic interactions are also demonstrated to be crucial factors for modulation of charge‐transport properties. The transfer integral undergoes slight changes under an applied electric field along the stacking direction in the range of 10⁶ ? 10⁷ V cm^?1. The change of central metals in MPc has little effect on the transfer integrals, but significantly affects the reorganization energies. The extension of the π‐conjugation in macrocyclic ligand brings about considerable influence on the transfer integrals. Peripheral substitutions by animo, hydroxyl, and methyl lead to deviations from planarity of macromolecular rings, and hence affect the valence bands significantly. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Darstellung und Eigenschaften der Diphthalocyaninate des Yttriums und Indiums

Synthesis and Properties of the Diphthalocyaninates of Yttrium and Indium Blue di(phthalocyaninato(2–))metalates of tervalent yttrium and indium are obtained by the reaction of yttrium acetate or anhydrous indium chloride with molten phthalodinitrile in the presence of potassium methylate and isolated as complex salts with organic cations. Anodic oxidation of (ⁿBu₄N)[M(Pc^2?)₂] (M = Y, In) yields crystals of green paramagnetic di(phthalocyaninato)metal(III)-dichloromethane solvate, [M(Pc)₂] · CH₂Cl₂ (μ_eff = 1.8/1.9 B.M. (Y/In)). Red brown di(phthalocyaninato)metal(III)-polybromide, [M(Pc^?)₂]Br_x is prepared by oxidation with bromine in excess. The redox properties of the di(phthalocyaninato)metalates(III) are investigated by cyclic voltammetry and difference pulse polarography. A quasi reversible (ΔE ? 60 mV) one electron process at 0.09 V (Y) and ?0.07 V (In) is assigned to the redox couple [M(Pc^2?)₂]^?/[M(Pc)₂]. Electronic absorption spectra as well as MIR/FIR and resonance Raman spectra are reported. The characteristic features of the three oxidation states and the influence of the ionic radius and the electron configuration of the metal ion are discussed.     

Electrochemical Impedance Spectroscopic Measurements of Sexithiophene—Effect of the Electrode Nature and the Dopant (CuCl2) Content

Electrochemical impedance spectroscopic (EIS) measurements of sexithiophene (6T) were carried out according to the Pt/6T/M sandwich structure configuration, for various electrode materials (M＝GC, ITO, Ag, Cu, Al) and for different doping levels of copper chloride (CuCl2). The results demonstrate that two types of charge transport are involved in the redox process at the electrode/6T interface and inside the bulk oligomer. The complex-plane impedance plots obtained for various doping levels of CuCl2 exhibit arc shapes. The charge-transfer resistance measured from the diagrams decreases systematically with the addition of the salt, leading to an increase of the oligothiophene conductivity.     

Transforming Ionene Polymers into Efficient Cathode Interlayers with Pendent Fullerenes

A new and highly efficient cathode interlayer material for organic photovoltaics (OPVs) was produced by integrating C₆₀ fullerene monomers into ionene polymers. The power of these novel “C₆₀‐ionenes” for interface modification enables the use of numerous high work‐function metals (e.g., silver, copper, and gold) as the cathode in efficient OPV devices. C₆₀‐ionene boosted power conversion efficiencies (PCEs) of solar cells, fabricated with silver cathodes, from 2.79 % to 10.51 % for devices with a fullerene acceptor in the active layer, and from 3.89 % to 11.04 % for devices with a non‐fullerene acceptor in the active layer, demonstrating the versatility of this interfacial layer. The introduction of fullerene moieties dramatically improved the conductivity of ionene polymers, affording devices with high efficiency by reducing charge accumulation at the cathode/active layer interface. The power of C₆₀‐ionene to improve electron injection and extraction between metal electrodes and organic semiconductors highlights its promise to overcome energy barriers at the hard‐soft materials interface to the benefit of organic electronics.     

Semiconducting poly(monocyanoacetylenes)

Poly(monocyanoacetylenes) (PMCA) were synthesized by anionic, Ziegler–Natta, metathesis, and photo initiations. The Ziegler–Natta-catalyzed polymers probably have highly stereoregular cis-transoid structure that contains very few defects and the nitrile groups are difficultly cyclized. It has M?_n = 1100. PMCA obtained by anionic polymerization at ?78°C has M?_n ～ 4800; it is rich in trans-transoid structures but probably contains other isomeric units as well. The unpaired spin concentrations in these polymers are very high, comparable to that in trans-polyacetylene (PA) isomerized above 150°C. UV irradiation initiated rapid polymerization of cyanoacetylene in solid state at low temperature but the products were bleached in color after long irradiation. The unpaired spins in PMCA are immobile; nitrile cyclization causes some decrease in EPR linewidth and increase in room-temperature conductivity (σ_RT). There was also a large increase in unpaired spin concentrations to about 200 monomer units/spin. Iodine doping increases σ_RT to about 10^?3 (ω cm)^?1 but the dopant is readily removed by evacuation and the polymer returns to its original insulating state. The properties of pristine and doped PMCA, such as EPR g-value, ΔH_pp, T₁, T₂, and σ_RT are very similar. The similarities persist after cyclization and doping for this pair of polymers. These properties are also compared with those of poly(methylacetylene), poly(phenylacetylene), poly(dicyanoacetylene) and PA, and the significance is discussed.     

High electrical conductivity for the partially oxidised d8 Ru–Ru bonded chain [Ru(bpy)(CO)2]n (bpy = 2,2′-bipyridine) and its wide range redox control

High, electrochemically controlled electrical conductivity (0.2–0.3 S cm^?1) was measured for the first time for the metal–metal bonded polymeric compound [Ru(bpy)(CO)₂]_n (bpy = 2,2′-bipyridine). The conductivity depended on the degree of partial oxidation of the initially zero-valent Ru to Ru^I in the chains and was found to increase by four orders of magnitude after 5% oxidative doping. Linear conductance vs. doping level dependence was found for low levels and the conductivity of films could repeatedly be switched on and off. The conduction process is ascribed to charge delocalisation on the Ru chains in analogy to that of other similar chains formed by stacking of planar transition metal d⁸ complexes.     

Overview of cationic phthalocyanines for effective photoinactivation of pathogenic microorganisms

Phthalocyanine (Pc) dyes are photoactive compounds that can absorb and emit light in a large range of the UV–vis spectrum, with recognized potential for medical applications. Considering the low solubility of Pc macrocycles in water, it is important to use cationic symptoms on their skeleton to improve their amphiphilicity for biomedical applications. The use of suitable pyridinium groups on Pc is a good strategy to solve this drawback and make them more eff ;ective to photoinactivate microorganisms via a photodynamic inactivation (PDI) approach. This review focuses the synthesis of quaternized Pc dyes, their photophysical and photochemical properties, and their antimicrobial photoinactivation efficiency. This innovative study compares, for the first time, different cationic moieties on Pc taking into account the efficiency of singlet oxygen (¹O₂), quantum yield (Φ_Δ) generation, fluorescence quantum yield (Φ_F), (photo)stability, light irradiation type (visible/white and/or red light), maximized overlapped absorption effect of Pc (S- and/or Q-band) vs light system irradiation type, and water solubility (n-octanol/water partition coefficient, P_o/w), when these parameters are determined and provided in the multidisciplinary reports. This approach is also relevant to conjugate free-base (H₂Pc) and metalated phthalocyanines (MPc, M = Zn²⁺, Mg²⁺, In³⁺, Ga³⁺, Ge³⁺, Si⁴⁺, etc.) with aromatic or aliphatic substituents linked by N, O or S atoms on the peripheral or axial positions of the Pc structures, such as e.g. (methoxy, oxy, or thio)pyridinium, ammonium, or benzimidazolium units, etc. Here, the influence of the structural peripheral (α- and/or β-position of Pc) or axial substituents type, number and positive charge position that can affect the PDI process will be analysed. These aspects are important to design versatile molecules that can interact with pathogenic microorganisms of variable size, subcellular architecture, biochemical composition, and susceptibility to externally added chemical agents. This review highlights the important developments of several modifications of cationic Pc dyes for the PDI of microorganisms, such as pathogenic bacteria, fungi, and virus.     

A novel efficient approach to heteronuclear triple-decker complexes of rare earth elements with phthalocyanines

A novel approach to heteroleptic heteronuclear rare earth metal(III) trisphthalocyaninates was proposed with the complexes [(15C5)₄Pc]M*[(15C5)₄Pc]M(Pc) as examples (15C5 is 15-crown-5, Pc^2? is the phthalocyaninate dianion, and M* ?? M = Yb and Y). Unsubstituted lanthanum bisphthalocyaninate, La(Pc)₂, was used for the first time as a Pc^2? donor in the synthesis of such complexes. This substantially increased the yields of the target heteronuclear complexes over the previous literature data.     

Influence of Peripheral Substitution on the Magnetic Behavior of Single‐Ion Magnets Based on Homo‐ and Heteroleptic TbIII Bis(phthalocyaninate)

A series of homoleptic ([Tb^III(Pc)₂]) and heteroleptic ([Tb^III(Pc)(Pc′)]) Tb^III bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert‐butyl or tert‐butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain electron‐donor moieties on one of the two Pc ligands show higher effective barriers and blocking temperatures than their homoleptic derivatives. This result is assigned to the elongation of the N? Tb distances in the substituted macrocycle, which brings the terbium(III) ion closer to the unsubstituted Pc, thus enhancing the ligand‐field effect. In particular, heteroleptic [Tb^III(Pc)(Pc′)] complex 4 , which contains one octa(tert‐butylphenoxy)‐substituted Pc ring and one bare Pc ring, exhibits the highest effective barrier and blocking temperature for a single‐molecule magnet reported to date.     

Methyloxy Substituted Heteroleptic Bis(phthalocyaninato) Yttrium Complexes: Density Functional Calculations

The effects of alkyloxy substituents attached to one phthalocyanine ligand of three heteroleptic bis(phthalocyaninato) yttrium complexes Y(Pc)[Pc(α‐OCH₃)₄] ( 1 ), Y(Pc)[Pc(α‐OCH₃)₈] ( 2 ), and Y(Pc)[Pc(β‐OCH₃)₈] ( 3 ), as well as their reduction products {Y(Pc)[Pc(α‐OCH₃)₄]}^? ( 4 ), {Y(Pc)[Pc(α‐OCH₃)₈]}^? ( 5 ), and {Y(Pc)[Pc(β‐OCH₃)₈]}^? ( 6 ) [H₂Pc(α‐OCH₃)₄=1,8,15,22‐tetrakis(methyloxy)phthalocyanine; H₂Pc(α‐OCH₃)₈=1,4,8,11,15,18,22,25‐octakis(methyloxy)phthalocyanine; H₂Pc(β‐OCH₃)₈=2,3,9,10,16,17,23,24‐octakis(methyloxy)phthalocyanine] are studied by DFT calculations. Good consistency is found between the calculated results and experimental data for the electronic absorption, IR, and Raman spectra of 1 and 3 . Introduction of electron‐donating methyloxy groups on one phthalocyanine ring of the heteroleptic double‐deckers induces structural deformation in both phthalocyanine ligands, electron transfer between the two phthalocyanine rings, changes in orbital energy and composition, shift of electronic absorption bands, and different vibrational modes of the unsubstituted and substituted phthalocyanine ligands in the IR and Raman spectra in comparison with the unsubstituted homoleptic counterpart Y(Pc)₂. The calculations reveal that incorporation of methyloxy substituents at the nonperipheral positions has greater influence on the structure and spectroscopic properties of bis(phthalocyaninato) yttrium double‐deckers than at the peripheral positions, which increases with increasing number of substituents. Nevertheless, the substituent effect of alkyloxy substituents at one phthalocyanine ligand of the double‐decker on the unsubstituted phthalocyanine ring and on the whole molecule and the importance of the position and number of alkyloxy substituents are discussed. In addition, the effect of reducing 1 – 3 to 4 – 6 on the structure and spectroscopic properties of the bis(phthalocyaninato) yttrium compounds is also discussed. This systemic DFT study is not only useful for understanding the structure and spectroscopic properties of bis(phthalocyaninato) rare earth metal complexes but also helpful in designing and preparing double‐deckers with tunable structure and properties.