Electrocrystallisation of (perylene)2[M(mnt)2] salts

Abstract

AbstractThe study of the family of compounds α‐(Per)2[M(mnt)2], (M = Cu, Au, Ni, Pd, Pt, Co, Fe) has started more than 30 years ago with the report of first members, but has been always limited by difficulties in the growth of high quality and large single crystals. These compounds can be obtained by oxidation of perylene in the presence of anion salts, either with iodine or electrochemically. The electrocrystallisation, which usually yields better quality crystals than the chemical oxidation route, has however several limitations and it is significantly more difficult to apply to these perylene compounds, which may present different stoichiometries and polymorphs, than to charge transfer salts of many other donors. These difficulties are associated with the low solubility of perylene and the instability of its radical cation in solution. The results of a systematic study to optimise the growth conditions of these compounds by electrocrystallisation and to identify key factors governing the formation of their different phases are presented. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)