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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
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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)4/3]·n(BzOH,ac) (1a(Bz,ac)) and [Fe(NCS)2(3-tpt)4/3]·n(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)2]·n(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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