On the existence of long C–C bonds between pairs of anions which repel: when and why? A test case on the [TCNE]22− dimers found in ionic crystals

Juan J. Novoa; Pilar Lafuente; Rico E. Del Sesto; Joel S. Miller

doi:10.1039/B202400B

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On the existence of long C–C bonds between pairs of anions which repel: when and why? A test case on the [TCNE]₂²⁻ dimers found in ionic crystals†

Juan J. Novoa,*^a Pilar Lafuente,^a Rico E. Del Sesto^b and Joel S. Miller*^b

Author affiliations

* Corresponding authors

^a Department of Physical Chemistry, University of Barcelona, Av. Diagonal, 647, Barcelona, Spain
E-mail: novoa@qf.ub.es

^b Department of Chemistry, University of Utah, 315 S. 1400 E. RM 2124, Salt Lake City, UT, USA
E-mail: jsmiller@chemistry.utah.edu

Abstract

Many of the C_m[TCNE]_n (C = cation) salts have intradimer C–C interactions in the range of 2.9 to 3.5 Å and show the electronic fingerprints associated with C–C bond formation (IR and UV spectra, magnetic properties, structural changes), despite the fact that two [TCNE]˙⁻ anions should repel each other due to purely Coulombic considerations. Herein, we analyze these pairwise interactions in detail for a particular crystal in which such a C–C bond is found, to understand when and why these bonds are formed in a general case.

This article is part of the themed collection: Innovation in Crystal Engineering

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Article information

DOI: https://doi.org/10.1039/B202400B
Article type: Paper
Submitted: 07 Mar 2002
Accepted: 02 May 2002
First published: 18 Jul 2002

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CrystEngComm, 2002,4, 373-377

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On the existence of long C–C bonds between pairs of anions which repel: when and why? A test case on the [TCNE]₂²⁻ dimers found in ionic crystals

J. J. Novoa, P. Lafuente, R. E. Del Sesto and J. S. Miller, CrystEngComm, 2002, 4, 373 DOI: 10.1039/B202400B

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