Australian Journal of Chemistry Australian Journal of Chemistry Society
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A Family of Three-Dimensional Molecular Framework Materials Containing the Three-Connecting Ligands 2,4,6-Tris(n′-pyridyl)-1,3,5-triazine: 3-tpt and 4-tpt

Suzanne M. Neville A , Gregory J. Halder B , Keith S. Murray A , Boujemaa Moubaraki A and Cameron J. Kepert C D

A School of Chemistry, Monash University, Vic. 3800, Australia.

B X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439, USA.

C School of Chemistry, The University of Sydney, NSW 2006, Australia.

D Corresponding author. Email: c.kepert@chem.usyd.edu.au

Australian Journal of Chemistry 66(4) 452-463 http://dx.doi.org/10.1071/CH12444
Submitted: 28 September 2012  Accepted: 9 December 2012   Published: 13 February 2013

Abstract

Three-dimensional (3D) framework materials containing the ligands 2,4,6-tris(4′-pyridyl)-1,3,5-triazine (4-tpt) and 2,4,6-tris(3′-pyridyl)-1,3,5-triazine (3-tpt) have been prepared and their structure and magnetic properties investigated. The [MII(NCS)2(py)4] (MII = Fe, Co, py = 3-tpt, and 4-tpt) coordination environments in these materials have been targeted in an effort to prepare high-dimensional coordination polymers which contain spin crossover (SCO) centres. Using FeII, two isotopological cubic 3D materials [Fe(NCS)2(4-tpt)4/3n(BzOH,ac) (1a(Bz,ac)) and [Fe(NCS)2(3-tpt)4/3n(BzOH,ac) (1b(Bz,ac)) were formed. However, with CoII a different 3D framework topology results, [Co(NCS)2(3-tpt)4/3]·(BzOH,ac) (2(Bz,ac)). Further synthetic variation leads to the isostructural 3D materials trans-[MII(NCS)2(4-tpt)4/3]cis-[MII(NCS)2(4-tpt)2n(tce, EtOH) (Fe: 3a(Tce,Et) and Co: 3b(Tce,Et)) which form 3D networks outside Wellsian classification – and for which uniquely both two- and three-connecting modes of 4-tpt are present in the one complex. Despite having the metal coordination environments for which SCO has previously been observed, magnetic susceptibilities of this family of materials reveal a high spin nature.


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