Architectural diversity in the solid-state behaviour of crown ether and [2.2.2]-cryptand complexes of K+TCNQ•‒ salts

Bingjia Yan, Peter N. Horton, Simon C. Weston, Chris Wedge, Andrea E. Russell, Martin C. Grossel

Research output: Contribution to journalArticlepeer-review


The solid-state behaviour of five ionophore-encapsulated TCNQ complexes: (18-crown-6)K(TCNQ)2.5 (1), ([2.2.2]-cryptand)K(TCNQ)2.5 (2), (benzo-18-crown-6)K(TCNQ)2 (3), (dibenzo-18-crown-6)K(TCNQ)2 (4), and (dicyclohexano-18-crown-6)K(TCNQ)3 (5) has been explored. For both 1 and 2, the TCNQ components assemble as a pentameric repeat unit within infinite TCNQ columns with the cation complex sitting in a cavity between the columns; whereas for 3 and 4, neighbouring (crown ether)K+ complexes form dimers involving K+-π interactions which further assemble into one-dimensional columns sitting between infinite TCNQ stacks. In the solid-state complex 5, the crown ether adopts a chair conformation with the resulting (crown ether)K+ complex assembling into a one-dimensional ladder. Pairs of TCNQ dimers separated by an isolated TCNQ unit form infinite TCNQ columns. IR and Raman spectroscopy reveal the presence of partially charged TCNQ units within all five TCNQ complexes (1-5) and resistivity studies indicate that all five TCNQ complexes (1-5) are more conductive than the corresponding simple KTCNQ salts. Preliminary EPR studies of 1 and 2 indicate typical behaviour of complex TCNQ salts (containing both TCNQ0 and TCNQ•‒).
Original languageEnglish
Pages (from-to)6705-6714
Number of pages10
Issue number38
Early online date1 Sep 2022
Publication statusPublished - 14 Oct 2022


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