Unraveling Coordination Features of Hemihexaphyrazines - New Approach to Perspective Materials for Nanoelectronics

Abstract

Hemihexaphyrazins are macrocycles containing three thiadiazole and three pyrrolecontaining subunits unified by an alternating fashion via six aza-bridges to form an expanded coordination cavity with 27-membered inner macroring bearing 9 nitrogen atoms. Due to such unusual structure to compare with porphyrins and phthalocyanines, hemihexaphyrazins have an enormous potential in coordination chemistry. It was established that they are able to hold 3 atoms of transition metals within inner cavity. Recently a clear evidence of such complexes formation was obtained by scanning tunneling microscopy (STM) [1]. Early using STM, unprecedented off-centered complexation motif of metal free hemihexaphyrazin (H3Hph) with dysprosium on Au(111) surface has been detected [2].Moreover, it was showed that due to presence of 9 nitrogen atoms within coordination cavity, H3Hph in reduced state can act as an aza-crown ether to form a new type of double-decker complex [3]. Partial charge transfer and uniform distribution of the charge over two macrocycles make these as promising building blocks for designing compounds with potential conducting and magnetic properties.Acknowledgement: this work was partially supported by Russian Foundation of Basic Research (project 19-03-00888) and Russian Science Foundation (project N 17-13-01215).Literature Bacilla Ana C. C., Okada Yusuke, Yoshimoto Soichiro, Islyaikin Mikhail K., Koifman Oskar I.; Kobayashi Nagao. Triangular Expanded Hemiporphyrazines: Electronic Structures and Nanoscale Characterization of Their Adlayers on Au(111). Bulletin of the Chemical Society of Japan. BCSJ. 2021, Vol.94, No.1, pp. 34 – 43. DOI: 10.1246/bcsj.20200188.Borja Cirera, Olga Trukhina, Jonas Björk, Giovanni Bottari, Jonathan Rodriguez-Fernandez, Alberto Martín-Jiménez, Mikhail K Islyaikin, Roberto Otero, José M. Gallego, Rodolfo Miranda, Tomas Torres, and David Ecija. Long-range orientational self-assembly, spatially-controlled deprotonation and off-centered metallation of an expanded porphyrin. J. Am. Chem. Soc., 2017, 139 (40), pp 14129–14136. DOI: 10.1021/jacs.7b06406.Dmitri Konarev, Salavat S. Khasanov, Mikhail K. Islyaikin, Akihiro Otsuka, Hideki Yamochi, Hiroshi Kitagawa, Rimma N. Lyubovskaya, Evgenii N. Ivanov, Oskar I. Koifman, Yuriy A. Zhabanov. Double-Decker Paramagnetic {(K)(H3Hhp)2}2- Radical Dianions Comprising Two [30]Trithia-2,3,5,10,12,13,15,20,22,23,25,30-Dodecaazahexaphyrins and a Potassium Ion. Chemistry – An Asian Journal. 2020, 15, 61 – 65. DOI: 10.1002/asia.201901518.