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Luminescent halogen-substituted 2-(N-arylimino)pyrrolyl boron complexes : the internal heavy-atom effect.

Rodrigues, Ana I. and Krishnamoorthy, Paramasivam and Gomes, Clara S. B. and Carmona, Nicolas and Di Paolo, Roberto E. and Pander, Piotr and Pina, João and Sérgio Seixas de Melo, J. and Dias, Fernando B. and Calhorda, Maria José and Maçanita, António L. and Morgado, Jorge and Gomes, Pedro T. (2020) 'Luminescent halogen-substituted 2-(N-arylimino)pyrrolyl boron complexes : the internal heavy-atom effect.', Dalton transactions., 49 (29). pp. 10185-10202.


A group of new boron complexes [BPh2{2N,N’-NC4H3-2-C(H)=N-C6H4X}] (X= 4-Cl 4c, 4-Br 4d, 4-I 4e, 3-Br 4f, 2-Br 4g, 2-I 4h) containing different halogens as substituents in the N-aryl ring have been synthesized and characterized in terms of their molecular properties. Their photophysical characteristics have been thoroughly studied in order to understand whether these compounds exhibit internal heavy atom effect. Phosphorescence emission was found for some of the synthesized halogen-substituted boron molecules, in particular for 4g and 4h. DFT and TDDFT calculations showed that the lower energy absorption band resulted from the HOMO to LUMO (-*) transition, except for 2-I 4h, where the HOMO-1 to LUMO transition was also involved. The strong participation of iodine orbitals in HOMO-1 is reflected on the calculated absorption spectra of the iodine derivatives, especially 2-I 4h, when spin-orbit coupling (SOC) was included. Organic light-emitting diodes (OLEDs) based on these compounds, in the neat form or dispersed in a matrix, were also fabricated and tested. The devices based on films prepared by thermal vacuum deposition showed the best performance. When neat compounds were used, a maximum luminance (Lmax) of 1812 cd m-2 was obtained, with maximum external quantum efficiency (EQEmax) of 0.15%. An EQEmax of ca. 1% along with a maximum luminance of 494 cd m-2 were obtained for a device fabricated by co-deposition of the boron complex and a host compound (1,3-bis(N-carbazolyl)benzene, mCP).

Item Type:Article
Full text:(AM) Accepted Manuscript
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Date accepted:29 June 2020
Date deposited:18 August 2020
Date of first online publication:29 June 2020
Date first made open access:29 June 2021

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