Capel Berdiell, I orcid.org/0000-0003-3828-7097, Farmiloe, SE, Kulmaczewski, R orcid.org/0000-0002-3855-4530 et al. (1 more author) (2019) Molecular Squares, Coordination Polymers and Mononuclear Complexes Supported by 2,4-Dipyrazolyl-6H-1,3,5-triazine and 4,6-Dipyrazolylpyrimidine Ligands. Dalton Transactions: an international journal of inorganic chemistry, 46. pp. 17310-17320. ISSN 1477-9226
Abstract
The Fe[BF4]2 complex of 2,4-di(pyrazol-1-yl)-6H-1,3,5-triazine (L1) is a high-spin molecular square, [{Fe(L1)}4(μ-L1)4][BF4]8, whose crystals also contain the unusual HPzBF3 (HPz = pyrazole) adduct. Three other 2,4-di(pyrazol-1-yl)-6H-1,3,5-triazine derivatives with different pyrazole substituents (L2-L4) are unstable in the presence of first row transition ions, but form mononuclear, polymeric or molecular square complexes with silver(I). Most of these compounds involve bis-bidentate di(pyrazolyl)triazine coordination, which is unusual for that class of ligand, and the molecular squares encapsulate one or two BF4‒, ClO4‒ or SbF6‒ ions through combinations of anion...π, Ag...X and/or C‒H...X (X = O or F) interactions. Treatment of Fe[NCS]2 or Fe[NCSe]2 with 4,6-di(pyrazol-1-yl)-2H-pyrimidine (L5) or its 2-methyl and 2-amino derivatives L6 and L7) yields mononuclear [Fe(NCE)2L2] and/or the 1D coordination polymers catena-[Fe(NCE)2(μ-L)] (E = S or Se, L = L5-L7). Alcohol solvates of isomorphous [Fe(NCS)2L2] and [Fe(NCSe)2L2] compounds show different patterns of intermolecular hydrogen bonding, reflecting the acceptor properties of the anion ligands. These iron compounds are all high-spin, although annealing solvated crystals of [Fe(NCSe)2(L5)2] affords a new phase exhibiting an abrupt, low-temperature spin transition. Catena-[Fe(H2O)2(μ-L5)][ClO4]2 is a coordination polymer of alternating cis and trans iron centres.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry. This is an author produced version of a paper published in Dalton Transactions. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Funding Information: | Funder Grant number EPSRC EP/K012568/1 Leverhulme Trust RPG-2015-095 |
Depositing User: | Symplectic Publications |
Date Deposited: | 06 Nov 2019 15:39 |
Last Modified: | 17 Dec 2024 15:12 |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/C9DT04003J |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:153115 |