Institut des Sciences et Technologies Moléculaires d'Angers

An overview of some recent developments of the chemistry of molecular donor materials for organic photovoltaics (OPV) is presented. Although molecular materials have been used for the fabrication of OPV cells from the very beginning of the field, the design of molecular donors specifically designed for OPV is a relatively recent research area. In the past few years, molecular donors have been used in both vacuum-deposited and solution-processed OPV cells and both fields have witnessed impressive progress with power conversion efficiencies crossing the symbolic limit of 10 %. However, this progress has been achieved at the price of an increasing complexity of the chemistry of active materials and of the technology of device fabrication. This evolution probably inherent to the progress of research is difficult to reconcile with the necessity for OPV to demonstrate a decisive economic advantage over existing silicon technology. In this short review various classes of molecular donors are discussed with the aim of defining possible basic molecular structures that can combine structural simplicity, low molecular weight, synthetic accessibility, scalability and that can represent possible starting points for the development of simple and cost-effective OPV materials.

This tutorial review presents some recent developments in the design, synthesis and implementation of organic solution-processable molecular fluorophores for non-doped electroluminescent [corrected] devices. After a brief presentation of the basic principles of operation and main characteristics of electroluminescent devices, some examples of active emitters representative of the main classes of non-doped molecular electrofluorophores will be discussed. Emphasis is placed on the relationships between the molecular structure and the electronic properties of molecular emitters, in which high photoluminescence efficiency, synthetic accessibility and processability are combined by design with additional functions such as hole and/or electron injection and transport.

This Review discusses the structure-property relationships in chiral molecules, macromolecules (polymers), and supramolecules (crystals, liquid crystals, or thin films) containing main-group elements. Chirality is a major property in our world, having a prominent influence on processes in biology, chemistry, and physics. Its impact in optics due to its interaction with electromagnetic waves gave rise to a multitude of effects, such as the Cotton effect and circularly polarized luminescence, making possible applications such as 3D displays and polarized sunglasses. Herein, a particular emphasis will be given to the influence of chirality on the conducting and optical properties of molecules or materials containing frontier heteroelements, particularly boron, silicon, phosphorus, and sulfur. These synergic materials are expected to become game-changers in the field of materials science by bringing new properties into the realm of reality, such as chirality-induced spin-selectivity, circularly polarized luminescence, and electrical magnetochiral anisotropy. This Review should be of interest for chemists and also physicists working in the fields of molecular and supramolecular chemistry, and molecular materials in the broadest sense.

Intense current interest in supramolecular chemistry is devoted to the construction of molecular assemblies displaying controlled molecular motion associated to recognition. On this ground, molecular clips and tweezers have focused an increasing attention. This tutorial review points out the recent advances in the construction of always more sophisticated molecular clips and tweezers, illustrating their remarkably broad structural variety and focusing on their binding ability towards neutral guests. A particular attention is brought to recent findings in dynamic molecular tweezers whose recognition ability can be regulated by external stimuli. Porphyrin-based systems will not be covered here as this very active field has been recently reviewed.

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The search for hybrid organic-inorganic materials, which have the great advantage that they can be synthesized at moderate temperature (T < 200 °C), remains a great challenge in the field of ferroelectrics. Here, a room-temperature ferroelectric material with interesting characteristics, (MV)[BiI(3)Cl(2)] (MV(2+) = methylviologen), is reported. Its structure is based on polar inorganic chains resulting from a remarkable Cl/I segregation induced by methylviologen entities, which coincide with the fourfold polar axis of the tetragonal structure. Of great importance is that this room-temperature hybrid ferroelectric displays a clear electrical hysteresis loop with a large spontaneous polarization (>15 μC·cm(-2)).

A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes such as thiadiazole-[7]helicene and bis(thiadiazole)-[8]helicene, to boost the oxygen evolution reaction (OER) by up to ca. 130 % (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D Ni- and NiFe-based catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given.

Fixation of a 5-hexyl-2,2'-bithienyl unit on a conjugated BODIPY donor increases the conversion efficiency of the resulting molecular bulk heterojunction solar cells from 1.30 to 2.20%.

The controlled preparation of chiral structures is a contemporary challenge for supramolecular science because of the interesting properties that can arise from the resulting materials, and here we show that a synthetic nonamphiphilic C(3) compound containing π-functional tetrathiafulvalene units can form this kind of object. We describe the synthesis, characterization, and self-assembly properties in solution and in the solid state of the enantiopure materials. Circular dichroism (CD) measurements show optical activity resulting from the presence of twisted stacks of preferential helicity and also reveal the critical importance of fiber nucleation in their formation. Molecular mechanics (MM) and molecular dynamics (MD) simulations combined with CD theoretical calculations demonstrate that the (S) enantiomer provides the (M) helix, which is more stable than the (P) helix for this enantiomer. This relationship is for the first time established in this family of C(3) symmetric compounds. In addition, we show that introduction of the "wrong" enantiomer in a stack decreases the helical reversal barrier in a nonlinear manner, which very probably accounts for the absence of a "majority rules" effect. Mesoscopic chiral fibers, which show inverted helicity, i.e. (P) for the (S) enantiomer and (M) for the (R) one, have been obtained upon reprecipitation from dioxane and analyzed by optical and electronic microscopy. The fibers obtained with the racemic mixture present, as a remarkable feature, opposite homochiral domains within the same fiber, separated by points of helical reversal. Their formation can be explained through an "oscillating" crystallization mechanism. Although C(3) symmetric disk-shaped molecules containing a central benzene core substituted in the 1,3,5 positions with 3,3'-diamido-2,2'-bipyridine based wedges have shown peculiar self-assembly properties for amphiphilic derivatives, the present result shows the benefits of reducing the nonfunctional part of the molecule, in our case with short chiral isopentyl chains. The research reported herein represents an important step toward the preparation of functional mesostructures with controlled helical architectures.

A novel stable bisazide molecule that can freeze the bulk heterojunction morphology at its optimized layout by specifically bonding to fullerenes is reported. The concept is demonstrated with various polymers: fullerene derivatives systems enable highly thermally stable polymer solar cells.

The structural and electronic properties of four isomers of didodecyl[1]-benzothieno[3,2-b][1]benzothiophene (C12-BTBT) have been investigated. Results show the strong impact of the molecular packing on charge carrier transport and electronic polarization properties. Field-induced time-resolved microwave conductivity measurements unravel an unprecedented high average interfacial mobility of 170 cm(2) V(-1) s(-1) for the 2,7-isomer, holding great promise for the field of organic electronics.

Controlling the guest expulsion process from a receptor is of critical importance in various fields. Several coordination cages have been recently designed for this purpose, based on various types of stimuli to induce the guest release. Herein, we report the first example of a redox-triggered process from a coordination cage. The latter integrates a cavity, the panels of which are based on the extended tetrathiafulvalene unit (exTTF). The unique combination of electronic and conformational features of this framework (i.e. high π-donating properties and drastic conformational changes upon oxidation) allows the reversible disassembly/reassembly of the redox-active cavity upon chemical oxidation/reduction, respectively. This cage is able to bind the three-dimensional B12 F12 (2-) anion in a 1:2 host/guest stoichiometry. The reversible redox-triggered disassembly of the cage could also be demonstrated in the case of the host-guest complex, offering a new option for guest-delivering control.

This review article gives an overview of past and current activities in the Linear Conjugated Systems Group of Angers and in the IPOC – Functional Polymers Group of the Institute of Polymer Chemistry of Stuttgart on the use of triphenylamine (TPA) as versatile building block for organic electronics. In the first part, the properties of TPA itself are introduced including geometrical and energy level considerations. Dimerization of TPA to tetraphenylbenzidine upon electrochemical oxidation is highlighted. The blocking of TPA para ‐positions and its implications in terms of electroactivity is further discussed. The second part shows that dimerization of TPA as pendant redox‐active moieties in polymers is a versatile strategy to crosslink polymer films. Coming from redox homopolymers the crosslinking strategy is extended towards conjugated redox polymers based on polythiophenes and block copolymers. Conductivity mechanisms and the influence of doping level on conductivity are probed with cyclic voltammetry coupled with in situ conductance and four‐point probe measurements. The last part is dedicated to the use of TPA as an electron‐donating block in the design of donor‐π‐acceptor chromophores and their use as active material in organic photovoltaics. An overview of some relevant TPA‐based push–pull molecules from the literature and our contribution to this field is presented emphasizing the progress of the photovoltaic performance of organic solar cells made over the last decade. © 2018 Society of Chemical Industry

Thiophene-based D-A-D π-conjugated systems containing triphenylamine end groups connected to a 1,1,4,4-tetracyanobuta-1,3-diene acceptor by oligothiophene chains of variable length have been synthesized. These compounds show interesting light-harvesting properties and low-lying HOMO levels. Preliminary results on bilayer heterojunction solar cells with C(60) as acceptor show power conversion efficiency higher than 1.0%.

Abstract An overview of various approaches for the realization of single‐material organic solar cells (SMOCs) is presented. Fullerene‐conjugated systems dyads, di‐block copolymers, and self‐organized donor‐acceptor molecules all represent different possible approaches towards SMOCs. Although each of them presents specific advantages and poses specific problems of design and synthesis, these different routes have witnessed significant progress in the past few years and SMOCs with efficiencies in the range of 1.50% have been realized. These performances are already higher than those of bi‐component bulk heterojunction solar cells some ten years ago, demonstrating that SMOCs can represent a credible approach towards efficient and simple organic solar cells. Possible directions for future research are discussed with the aim of stimulating further research on this exciting topic.

A functionalized polymer film allowing for a complete and straightforward second-harmonic generation (SHG)-assisted high-contrast writing-reading-erasing-writing sequence is proposed. The whole process is supported by the reversible photoinduced dimerization of a coumarin chromophore and enables efficient optical data storage that can be detected only by SHG imaging.

Single material organic solar cells (SMOSCs) are based on ambivalent materials containing electron donor (D) and acceptor (A) units capable to ensure the basic functions of light absorption, exciton dissociation, and charge transport. Compared to bicomponent bulk heterojunctions, SMOSCs present several major advantages such as considerable simplification of cell fabrication and a strong stabilization of the morphology of the D/A interface, and thus of the cell lifetime. In addition to these technical issues, SMOSCs pose fundamental questions regarding the possible formation, and dissociation of excitons on the same molecular D-A architecture. SMOSCs are developed with various approaches, namely "double-cable" polymers, block copolymers, oligomers, and molecules that differ by the donor platform: polymer or molecule, the nature of A, the D-A connection, and the intra- and intermolecular interactions of D and A. Although for several years the maximum efficiency of SMOSCs has remained limited to 1.0-1.5%, impressive progress has been recently accomplished leading to SMOSCs with 4.0-5.0% efficiency. Here, recent advances in the synthesis of D-A materials for SMOSCs are presented in the broader context of the chemistry of organic photovoltaic materials in order to discuss possible directions for future research.

A simple strategy to avoid the formation of polyaryl layer during the functionalization of carbon surface by diazonium electroreduction is presented. The approach proposes to directly act on the polymerization mechanism by the use of a radical scavenger. The kinetic gap between the surface coupling and the multilayer formation is exploited to prevent the growth of the layer without interfering with the grafting. The well-known 4-nitrobenzenediazonium electrografting was used to demonstrate the possibility of reaching a monolayer surface coverage with an excess of DPPH (2,2-diphenyl-1-picrylhydrazyl). Experimental conditions were varied to validate the efficiency of the grafting limitation and the radical capture was confirmed by isolation of the aryl radical/DPPH coupling product.

Abstract Luminescent solar concentrators (LSCs) are optical systems that absorb, convert, and concentrate solar light by means of photoluminescence of an emitting material embedded in a transparent waveguide. LSCs combine large possibilities of variation of shape, flexibility, color, and transparency and can operate under direct or diffuse light. LSCs were actively investigated in the period 1975–1985 in view of photovoltaic (PV) conversion. After 20 years of sleep, research on LSCs has reemerged in the first years of the millennium driven by their potential application for PV conversion in built environment. Research on LSCs aims at the development of new active and passive components, namely emitting and light‐guiding materials, and at the reduction of the loss factors associated with the elemental processed involved in the operation in order to improve power conversion efficiency. After a brief historical account, the operating principles, characterization, components, technology, and applications are reviewed. Finally, the performance of LSCs are critically discussed in a global perspective with particular emphasis on the basic contradiction between light concentration and conversion efficiency leading to some suggestions for future development of the topic.

Syntheses, X-ray structural analyses, thermal behaviors, photochromism, and electrical properties of a series of methylviologen (MV(2+)) halobismuthate hybrids, namely, (MV)(3)[Bi(4)Cl(18)](H(2)O)(y) (1a, y approximately = 1.7), (MV)(4)[Bi(6)Cl(26)](H(2)O)(y) (2a, y approximately = 1.7), (MV)(4)[Bi(6)Cl(25.6)I(0.4)](H(2)O)(y) (3a, y approximately = 1.5), and (MV)(4)[Bi(6)Cl(24.6)I(1.4)](H(2)O)(y) (4a, y approximately = 1.3), are reported. Because of the thermal effect of a UV lamp or as a result of being heated up to 100 degrees C, all of the above compounds undergo a complete (1a, 2a, and 3a) or a partial (4a) dehydration together, in 2a and 3a, with an impressive structural reorganization involving a 90 degrees rotation of methylviologen dimers and, in 3a, a new Cl/I distribution, finally leading to (MV)(3)[Bi(4)Cl(18)] (1b), (MV)(4)[Bi(6)Cl(26)] (2b), (MV)(4)[Bi(6)Cl(25.6)I(0.4)] (3b), and (MV)(4)[Bi(6)Cl(24.6)I(1.4)](H(2)O)(x) (4a, x approximately = 0.65), respectively. In its turn, 4a (x approximately = 0.65) undergoes an abrupt structural change at 160 degrees C when water molecules are completely removed, leading to (MV)(4)[Bi(6)Cl(24.6)I(1.4)] (4b). Obviously, the two first dehydrated phases can be considered as the n = 2 (1b) and n = 3 (2b) members of the (MV)((2n+2)/2)[Bi(2n)Cl(8n+2)] family, and the ultimate member (n = infinity) with an infinite 1D double-chain inorganic framework, namely, (MV)[Bi(2)Cl(8)], has already been reported. According to the results of structural refinements, some positions of the Cl atoms in the [Bi(6)Cl(26)](8-) anionic cluster of 3a and 4a have been occupied by I atoms, finally leading to iodide-doped materials of the 2a type (percentage of doping: 3a, 1.5%; 4a, 5.4%). Upon UV irradiation, yellow crystals of 2a and 3a (which become 2b and 3b because of the thermal effect of the UV lamp) or yellow crystals of 2b, 3b, and 4a undergo a color change to black crystals (in the case of 2b), as observed in (MV)[Bi(2)Cl(8)], or light-brown crystals (in the cases of 3b and 4a). These photochromic properties are probably due to the photoinduced electron transfer from the anionic part to the methylviologen dications. In contrast, no color change is observed when yellow crystals of 1a or 1b and the iodide-doped (MV)[Bi(2)Cl(8-epsilon)I(epsilon)] material are irradiated. Because the relative positions of methylviologen to the host anionic frameworks are comparable in all structures (the N...Cl distances are about 3.4 A), these results indicate that such kinds of photochemical reactions depend on the dimension of the anionic networks, as well as the iodide doping. The single-crystal electrical conductivity measurements of 2b before and after irradiation were carried out between 150 and 393 K. The results prove that both of them are semiconductors with weak room temperature conductivity and that the band gap of the irradiated crystal (2b, 0.35 eV) is much smaller than that of the original hybrid 2a (1.0 eV).