Issue 21, 2012

Preparation and superconductivity of intercalation compounds of TiNCl with aliphatic amines

Abstract

Intercalation compounds of TiNCl with n-alkyl monoamines (CnH2n+1NH2, 3 ≤ n ≤ 12) and alkylene diamines (H2NCnH2nNH2, 2 ≤ n ≤ 12) have been prepared. Upon intercalation of monoamines, the basal spacing of TiNCl expanded from 7.8 Å to a value in the range of 12.0 to 37 Å, with the alkyl chains oriented in various ways; the stacking of TiNCl layers became turbostratic disordered. Diamines show only a limited expansion of the basal spacing in a range of 11.1 to 12.3 Å with the alkylene chains oriented parallel to TiNCl layers which are mutually shifted along the a- and b-axes in the ab plane, and stacked to form new polytypes with the space group Bmmb or Immm different from Pmmn of the pristine TiNCl. Only diamine intercalated compounds showed superconductivity with the transition temperatures (Tc's) ranging from 6.8 to 17.1 K. The intercalation compounds with diamine molecules with longer alkylene chains tend to exhibit higher Tc's; the compounds with diamines with an even number of carbon atoms tend to have larger superconducting volume fractions. Superconductivities of the intercalation compounds with N,N′-substituted alkylene diamines have been examined, which also showed superconductivity with Tc's in the range of 8.6–15.8 K. It is likely that the charge transfer of the lone pair electrons of amino groups may change the semiconductor TiNCl to superconductors with ordered stacking structures.

Graphical abstract: Preparation and superconductivity of intercalation compounds of TiNCl with aliphatic amines

Supplementary files

Article information

Article type
Paper
Submitted
29 Nov 2011
Accepted
22 Mar 2012
First published
23 Apr 2012

J. Mater. Chem., 2012,22, 10752-10762

Preparation and superconductivity of intercalation compounds of TiNCl with aliphatic amines

S. Yamanaka, K. Umemoto, Z. Zheng, Y. Suzuki, H. Matsui, N. Toyota and K. Inumaru, J. Mater. Chem., 2012, 22, 10752 DOI: 10.1039/C2JM16225C

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