Miriam Más-Montoya

Indolocarbazole-based ligands for ladder-type four-coordinate boron complexes.

A novel class of π-conjugated systems, which combine the indolo[3,2-b]carbazole unit with the formation of four-coordinate boron complexes, is presented. The resulting conjugated compounds have a double-laddered structure that provides interesting optical and electrochemical properties. The wide absorption range, covering most of the visible spectrum, along with the narrowing of the HOMO-LUMO energy gap, due to the presence of diphenylboryl centers, reinforces the potential of these molecules within the area of organic electronics.

Isomeric carbazolocarbazoles: synthesis, characterization and comparative study in Organic Field Effect Transistors

We report here the synthesis and characterization of a new family of isomeric carbazolocarbazole derivatives, namely carbazolo[1,2-a]carbazole, carbazolo[3,2-b]carbazole and carbazolo[4,3-c]carbazole. Thermal, optical, electrochemical, morphological and semiconducting properties have been studied to understand the influence of geometrical isomerism on the optoelectronic properties of these compounds. Different packing patterns have been observed by single crystal X-ray diffraction (XRD) which then correlate with the different morphologies of the evaporated thin films studied by XRD and Atomic Force Microscopy (AFM). The effect of N-substituents has also been evaluated for one of the isomers revealing a noticeable influence on the performance as organic semiconductors in Organic Field Effect Transistors (OFETs). A good p-channel field effect has been determined for N,N′-dioctylcarbazolo[4,3-c]carbazole with a mobility of 0.02 cm2 V−1 s−1 and Ion/Ioff ratio of 106 in air. These preliminary results demonstrate the promising properties of molecular carbazolocarbazole systems which should be further explored in the area of organic semiconducting materials.

Multifunctional carbazolocarbazoles as hole transporting and emitting host materials in red phosphorescent OLEDs

A new series of carbazolo[4,3-c]carbazoles (1–3) have been examined as hole-transporting and emitting host materials in the fabrication of red phosphorescent OLEDs (PhOLEDs). The presence of different N-substituents including hydrogen, octyl and 4-butylphenyl attached to the carbazolo[4,3-c]carbazole skeleton was aimed to condition the charge transporting properties. Due to their resemblance in the electronic structure, these carbazolocarbazoles have been compared to a commonly used hole-transporting material such as N,N′-bis(naphthalen-1-yl)-N,N′-bisphenylbenzidine (NPB). Interestingly, the introduced structural differences endow compounds 1–3 with a wide range of hole-mobilities, which provide room for adjusting the carrier balance of OLEDs. Different approaches, including bi-layer and tri-layer architectures, have been employed for the successful fabrication of Ir(piq)2(acac) doped OLEDs using NPB and these novel carbazolocarbazoles as hole transport and host materials. The simplified bi-layer device demonstrated high performance with maximum efficiencies of 8.7%, 5.6 cd A−1 and 3.4 lm W−1 when using the N-alkylated derivative 2. Furthermore, the red PhOLEDs with tri-layer architecture using 3 as the HTL showed peak efficiencies of 12.2%, 8.7 cd A−1, and 9.3 lm W−1. In addition, both compounds 2 and 3 used in OLEDs exhibited superior performance to those of devices using NPB, demonstrating their high potential for employment in phosphorescent OLEDs.

Synthesis and Characterization of New Carbazolocarbazoles: Toward π-Extended N-Fused Heteroacenes

A regiospecific route has been developed for the synthesis of carbazolo[1,2-a]carbazole. The synthetic strategy is based on the use of appropriately tetrasubstituted naphthalene. Optical and electrochemical characterization of the fused heteroaromatic system reveals that this optically transparent heteroacene, with a low-lying HOMO, might be used as an organic material.

Single Heteroatom Fine-Tuning of the Emissive Properties in Organoboron Complexes with 7-(Azaheteroaryl)indole Systems

The application of organoboron compounds as light-absorbing or light-emitting species in areas as relevant as organic electronics or biomedicine has motivated the search for new materials which contribute to the progress of those applications. This article reports the synthesis of four-coordinate boron complexes based on the unexplored 7-(azaheteroaryl)indole ligands. An easy synthetic approach has enabled the fine-tuning of the electronic structure of the organoboron species by modifying a heteroaromatic component in the conjugated system. Furthermore, a comprehensive characterization by X-ray diffraction, absorption and emission spectroscopy, both in solution and in the solid state, cyclic voltammetry, and computational methods has evidenced the utility of this simple strategy. Large Stokes shifts have been achieved in solid thin-films which show a range of emitted light from blue to orange. The synthesized compounds have been used as biocompatible fluorophores in cell bioimaging.

New carbazolo[1,2-a]carbazole derivative as ionophore for anion-selective electrodes: remarkable recognition towards dicarboxylate anions.

A new carbazolo[1,2-a]carbazole derivative was synthesized by expanding the binding cavity to explore the possibility of hosting larger anions such as dicarboxylate anions. The compound was incorporated as an ionophore into a membrane for an anion-selective electrode. The response of the electrode was evaluated for oxalate, malonate, succinate, glutarate and adipate in terms of calibration characteristics (slope, limit of detection and linear range of the response), response time, repeatability, reproducibility and selectivity. Nernstian reproducible responses, with very good detection limits, fast responses and selectivity not previously observed, were found for all the dicarboxylates anions, and the results were especially good in the case of glutarate. In order to obtain additional structural information about the complex formed between the ionophore and the dicarboxylate anions, (1)H NMR and fluorescence studies were carried out. The observed potentiometric selectivity depends on the good correspondence between the size of the carbazolocarbazole cavity and the length of the dicarboxylate anion, as supported by the NMR and fluorescence studies.

Benzodipyrrole derivates as new ionophores for anion-selective electrodes: Improving potentiometric selectivity towards divalent anions

Two open substituted benzodipyrroles were tested as hydrogen-bond-forming anion ionophores for the development of anion-selective electrodes. These compounds were incorporated in plasticized polymeric membranes with different plasticizers, using different membrane compositions to explore their response towards several anions. The electrodes constructed with membranes containing 2-nitrophenyl octyl ether and a 0.5 molar ratio ionic additive/ionophore showed pronounced anti-Hofmeister behaviour, providing a significantly enhanced response towards the divalent anions sulfate, sulfite, thiosulfate and oxalate. The selected electrodes were also evaluated in terms of detection limits and selectivity. (1)H NMR experiments were carried out in an attempt to explain some aspects of the behaviour observed.

Synthesis and characterization of carbazolo[2,1-a]carbazole in thin film and single crystal field-effect transistors

The synthesis of a hexacyclic fused polyheteroaromatic system, namely carbazolo[2,1-a]carbazole, via a simple two-step route is reported. Additionally, the characterization of its electronic structure is described, corresponding to a very stable molecule that is also transparent to visible light. Solid state packing is determined by X-ray diffraction analysis which, in combination with the computational calculation of the charge transfer parameters, reveals an adequate molecular arrangement to achieve a low anisotropic environment for charge transport. This π-conjugated system is used as an organic semiconductor for the fabrication of thin film and single crystal organic field-effect transistors (OFETs). Furthermore, the evaluation of different gate dielectrics results in transistors with very good hole mobilities and low operating voltages. In agreement with these results, carbazolo[2,1-a]carbazole becomes one of the best organic semiconductors belonging to the family of carbazole-based azaphenacenes.

Conductivity and nanoscale morphology of thin films prepared from indolo[2,3-a]carbazole and 11,12-dioctylindolo[2,3-a]carbazole

A systematic study on the thin film morphology of heteroacenic derivatives such as indolo[2,3-a]carbazole and 11,12-dioctylindolo[2,3-a]carbazole has been carried out using scanning force microscopy and optical microscopy techniques. The investigation has comprised the preparation of a series of thin films by combining different solvents (dimethylformamide and tetrahydrofurane), substrates (glass, gold, silicon and aluminium) and deposition techniques (spin coating and thermal evaporation) we found a wide variety of self-assembled structures. In addition, conductivity measurements have been performed, showing a very large spread in conductivity values. Some of the samples give quite high conductivity while others conduct very poorly, even in the case of samples prepared with essentially the same conditions. These results indicate that morphology is very critical for the final conductivity of the thin films. In addition we conclude that for some of the films prepared the homogeneous thin film approximation must be revised otherwise obtained conductivity measurements lead to significant error.