Grafting Electron-Accepting Fragments on [4]cyclo-2,7-carbazole Scaffold: Tuning the Structural and Electronic Properties of Nanohoops.

Since the first applications of nanohoops in organic electronics appear promising, the time has come to go deeper into their rational design in order to reach high-efficiency materials. To do so, systematic studies dealing with the incorporation of electron-rich and/or electron-poor functional units on nanohoops have to be performed. Herein, the synthesis, the electrochemical, photophysical, thermal, and structural properties of two [4]cyclo-2,7-carbazoles, [4]C-Py-Cbz, and [4]C-Pm-Cbz, possessing electron-withdrawing units on their nitrogen atoms (pyridine or pyrimidine) are reported. The synthesis of these nanohoops is first optimized and a high yield above 50% is reached. Through a structure-properties relationship study, it is shown that the substituent has a significant impact on some physicochemical properties (eg HOMO/LUMO levels) while others are kept unchanged (eg fluorescence). Incorporation in electronic devices shows that the most electrically efficient Organic Field-Effect transistors are obtained with [4]C-Py-Cbz although this compound does not present the best-organized semiconductor layer. These experimental data are finally confronted with the electronic couplings between the nanohoops determined at the DFT level and have highlighted the origin in the difference of charge transport properties. [4]C-Py-Cbz has the advantage of a more 2D-like transport character than [4]C-Pm-Cbz, which alleviates the impact of defects and structural organization.

Memory Effect by Melt Crystallization Observed in Polymorphs of a Benzothieno-Benzothiophene Derivative.

This work provides a comprehensive illustration of a crystalline melt memory effect recorded for three solvates of the 2,7-bis(2-(2-methoxyethoxy)ethoxy)benzo[b]benzo[4,5] thieno[2,3-d]thiophene (OEG-BTBT) molecule with dichloromethane (DCM) molecules. Combined optical microscopy and X-ray diffraction measurements at different temperatures are used to get an overview of the structural and morphological properties like melting points, isotropic transition temperatures, induction times, and crystallization kinetics of the three forms. An outstanding observation is made upon annealing the three polymorphs at temperatures well above their respective melting points as well as above the optical clearance temperature. After cooling back to room temperature, recrystallization results in the formation of the initial phase present before the annealing process. This melt memory effect is observed for all three solvates. These observations can be correlated to the strong interaction between the DCM molecules and the oligoethylene glycol side chains, even in the molten state. This conclusion rationalizes the experimental observation made upon solvent vapor annealing of the crystalline sample with DCM, which unambiguously transformed the system into a disordered state.

Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs.

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.

Polymorph screening at surfaces of a benzothienobenzothiophene derivative: discovering new solvate forms.

The discovery of new polymorphs opens up unique applications for molecular materials since their physical properties are predominantly influenced by the crystal structure type. The deposition of molecules at surfaces offers great potential in the variation of the crystallization conditions, thereby allowing access to unknown polymorphs. With our surface crystallization approach, four new phases are found for an oligoethylene glycol-benzothienobenzothiophene molecule, and none of these phases could be identified via classical polymorph screening. The corresponding crystal lattices of three of the new phases were obtained via X-ray diffraction (XRD). Based on the volumetric considerations together with X-ray fluorescence and Raman spectroscopy data, the phases are identified as solvates containing one, two or three solvent molecules per molecule. The strong interaction of dichloromethane with the oligoethylene glycol side chains of the molecules may be responsible for the formation of the solvates. Temperature-dependent XRD reveals the low thermal stability of the new phases, contrary to the thermodynamically stable bulk form. Nevertheless, the four solvates are stable under ambient conditions for at least two years. This work illustrates that defined crystallization at surfaces enables access to multiple solvates of a given material through precise and controlled variations in the crystallization kinetics.

Electronic and Charge Transport Properties in Bridged versus Unbridged Nanohoops: Role of the Nanohoop Size.

In the field of π-conjugated nanohoops, the size of the macrocycle has a strong impact on its structural characteristics, which in turn affect its electronic properties. In this work, we report the first experimental investigations linking the size of a nanohoop to its charge transport properties, a key property in organic electronics. We describe the synthesis and study of the first example of a cyclocarbazole possessing five constituting building units, namely [5]-cyclo-N-butyl-2,7-carbazole, [5]C-Bu-Cbz. By comparison with a shorter analogue, [4]-cyclo-N-butyl-2,7-carbazole, [4]C-Bu-Cbz, we detail the photophysical, electrochemical, morphological and charge transport properties, highlighting the key role played by the hoop size. In particular, we show that the saturated field effect mobility of [5]C-Bu-Cbz is four times higher than that of its smaller analogue [4]C-Bu-Cbz (4.22×10-5 vs 1.04×10-5  cm2 V-1 s-1 ). However, the study of the other organic field-effect transistor characteristics (threshold voltage VTH and subthreshold slope SS) suggest that a small nanohoop is beneficial for good organization of the molecules in thin films, whereas a large one increases the density of structural defects, and hence of traps for the charge carriers. The present findings are of interest for the further development of nanohoops in electronics.

Pure Hydrocarbon Materials as Highly Efficient Host for White Phosphorescent Organic Light-Emitting Diodes: A New Molecular Design Approach.

To date, all efficient host materials reported for phosphorescent OLEDs (PhOLEDs) are constructed with heteroatoms, which have a crucial role in the device performance. However, it has been shown in recent years that the heteroatoms not only increase the design complexity but can also be involved in the instability of the PhOLED, which is nowadays the most important obstacle to overcome. Herein, we design pure aromatic hydrocarbon materials (PHC) as very efficient hosts in high-performance white and blue PhOLEDs. With EQE of 27.7 %, the PHC-based white PhOLEDs display similar efficiency as the best reported with heteroatom-based hosts. Incorporated as a host in a blue PhOLED, which are still the weakest links of the technology, a very high EQE of 25.6 % is reached, surpassing, for the first time, the barrier of 25 % for a PHC and FIrpic blue emitter. This performance shows that the PHC strategy represents an effective alternative for the future development of the OLED industry.

Dinaphthotetrathienoacenes: Synthesis, Characterization, and Applications in Organic Field-Effect Transistors.

The charge transport of crystalline organic semiconductors is limited by dynamic disorder that tends to localize charges. It is the main hurdle to overcome in order to significantly increase charge carrier mobility. An innovative design that combines a chemical structure based on sulfur-rich thienoacene with a solid-state herringbone (HB) packing is proposed and the synthesis, physicochemical characterization, and charge transport properties of two new thienoacenes bearing a central tetrathienyl core fused with two external naphthyl rings: naphtho[2,3-b]thieno-[2''',3''':4'',5'']thieno[2″,3″:4',5']thieno[3',2'-b]naphtho[2,3-b]thiophene (DN4T) and naphtho[1,2-b]thieno-[2''',3''':4'',5'']thieno[2'',3'':4',5']thieno[3',2'-b]naphtho[1,2-b]thiophene are presented. Both compounds crystallize with a HB pattern structure and present transfer integrals ranging from 33 to 99 meV (for the former) within the HB plane of charge transport. Molecular dynamics simulations point toward an efficient resilience of the transfer integrals to the intermolecular sliding motion commonly responsible for strong variations of the electronic coupling in the crystal. Best device performances are reached with DN4T with hole mobility up to µ = 2.1 cm2 V-1 s-1 in polycrystalline organic field effect transistors, showing the effectiveness of the electronic coupling enabled by the new aromatic core. These promising results pave the way to the design of high-performing materials based on this new thienoacene, notably through the introduction of alkyl side-chains.

[4]Cyclo-N-alkyl-2,7-carbazoles: Influence of the Alkyl Chain Length on the Structural, Electronic, and Charge Transport Properties.

Macrocycles possessing radially oriented π-orbitals have experienced a fantastic development. However, their incorporation in organic electronic devices remains very scarce. In this work, we aim at bridging the gap between organic electronics and nanorings by reporting the first detailed structure-properties-device performance relationship study of organic functional materials based on a nanoring system. Three [4]cyclo-N-alkyl-2,7-carbazoles bearing different alkyl chains on their nitrogen atoms have been synthesized and characterized by combined experimental and theoretical approaches. This study includes electrochemical, photophysical, thermal, and structural solid-state measurements and charge transport properties investigations. An optimized protocol of the Pt approach has been developed to synthesize the [4]cyclocarbazoles in high yield (52-64%), of great interest for further development of nanorings, especially in materials science. The charge transport properties of [4]cyclocarbazoles and model compound [8]cycloparaphenylene ([8]CPP) have been studied. Although no field effect (FE) mobility was recorded for the benchmark [8]CPP, FE mobility values of ca. 10-5 cm2·V-1·s-1 were recorded for the [4]cyclocarbazoles. The characteristics (threshold voltage VTH, subthreshold swing SS, trapping energy ΔE) recorded for the three [4]cyclocarbazoles appear to be modulated by the alkyl chain length borne by the nitrogen atoms. Remarkably, the space-charge-limited current mobilities measured for the [4]cyclocarbazoles are about 3 orders of magnitude higher than that of [8]CPP (1.37/2.78 × 10-4 cm2·V-1·s-1 for the [4]cyclocarbazoles vs 1.21 × 10-7 cm2·V-1·s-1 for [8]CPP), highlighting the strong effect of nitrogen bridges on the charge transport properties. The whole study opens the way to the use of nanorings in electronics, which is now the next step of their development.