277 research outputs found
The Effect of Ligand Design on Metal Ion Spin State - Lessons from Spin Crossover Complexes
No full textThe relationship between chemical structure and spin state in a transition metal complex has an important bearing on mechanistic bioinorganic chemistry, catalysis by base metals, and the design of spin crossover materials. The latter provide an ideal testbed for this question, since small changes in spin state energetics can be easily detected from shifts in the spin crossover equilibrium temperature. Published structure-function relationships relating ligand design and spin state from the spin crossover literature give varied results. A sterically crowded ligand sphere favors the expanded metal–ligand bonds associated with the high-spin state. However, steric clashes at the molecular periphery can stabilize either the high-spin or the low-spin state in a predictable way, depending on their effect on ligand conformation. In the absence of steric influences, the picture is less clear since electron-withdrawing ligand substituents are reported to favor the low-spin or the high-spin state in different series of compounds. A recent study has shed light on this conundrum, showing that the electronic influence of a substituent on a coordinated metal ion depends on its position on the ligand framework. Finally, hydrogen bonding to complexes containing peripheral N–H groups consistently stabilizes the low-spin state, where this has been quantified
Insight into structure: function relationships in a molecular spin-crossover crystal, from a related weakly cooperative compound
No full textThis is a repository copy of Insight into structure: function relationships in a molecular spin-crossover crystal, from a related weakly cooperative compound. White Rose Research Online URL for this paper: http://eprints.whiterose.ac.uk/83008/ Version: Accepted Version Article: Elhaïk, J, Kilner, C and Halcrow, MA (2014) Insight into structure: function relationships in a molecular spin-crossover crystal, from a related weakly cooperative compound. European Journal of Inorganic Chemistry, 2014 (26). 4250 -4253. ISSN 14344250 -4253. ISSN -1948 https://doi.org/10.1002/ejic.201402623 [email protected] https://eprints.whiterose.ac.uk/ Reuse Unless indicated otherwise, fulltext items are protected by copyright with all rights reserved. The copyright exception in section 29 of the Copyright, Designs and Patents Act 1988 allows the making of a single copy solely for the purpose of non-commercial research or private study within the limits of fair dealing. The publisher or other rights-holder may allow further reproduction and re-use of this version -refer to the White Rose Research Online record for this item. Where records identify the publisher as the copyright holder, users can verify any specific terms of use on the publisher's website. Takedown If you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing [email protected] including the URL of the record and the reason for the withdrawal request. Insight into Compound Jérôme Elhaïk, [a] Colin A. Kilner, [a] and Malcolm A. Halcrow* [a] Abstract: The ClO4 − salt of [FeL2] 2+ (L = 2,6-bis(3-methylpyrazol-1-yl)pyridine) undergoes very gradual thermal spin-crossover centered just below room temperature. In contrast, the BF4 − salt of the same complex exhibits an abrupt and structured spin-transition at lower temperature, with a complicated structural chemistry. The difference can be attributed to a much larger change in molecular structure between the spin states of the complex in the more cooperative BF4 − salt, leading to an increased kinetic barrier for their interconversion. Consistent with that suggestion, the high-spin and low-spin structures of weakly cooperative [FeL2][ClO4]2 are almost superimposable. The continuing interest in thermally and optically switchable spin-crossover (SCO) materials [9] Its thermal spin-transition takes place in two steps, via a re-entrant symmetry-breaking transition to an intermediate crystal phase, with a tripled unit cell containing a mixture of high-spin and low-spin sites. The first of these steps occurs abruptly with hysteresis, but at a temperature that varies according to the water content of the sample (x). In contrast the second step is kinetically slow, and is only achieved when the sample is poised at 100 K for 1.5 hrs. [10] Its excited spin-state trapping (LIESST [11] ) behavior is also unique, in that its thermodynamic high low spin transition and kinetically controlled high low spin-state relaxation exhibit different profiles and are effectively decoupled from each other. [12] Although unexceptional in itself, 1[ClO4]2 provides useful insight into the structural origin of the unusual behavior of the BF4 − salt by providing a rare comparison between strongly and weakly cooperative spin-crossover materials based on the same complex molecule. At 300 K, MT for 1[ClO4]2 is 2.4 cm 3 mol -1 K, lower than expected for a high-spin iron(II) complex with this ligand type (3.4-3.6 cm 3 mol -1 K)
Photomagnetic studies on spin-crossover solid solutions containing two different metal complexes, [Fe(1-bpp)2]x[M(terpy)2]1?x[BF4]2 (M = Ru or Co)
No full textThe photomagnetic properties of two series of spin-crossover solid solutions, [Fe(1-bpp)(2)](x)[Ru(terpy)(2)](1-x)(BF4)(2) and [Fe(1-bpp)(2)](x)[Co(terpy)(2)](1-x)(BF4)(2) (1-bpp = 2,6-bis[pyrazol-1-yl]pyridine), have been investigated. For all the materials, the evolution of the T(LIESST) value, the high-spin -> low-spin relaxation parameters and the LITH loops were thoroughly studied. Interestingly in the Fe : Co series, along the photo-excitation, cobalt ions are concomitantly converted from low-spin to high-spin states with the iron centres, and also fully relax after light excitation
Interpreting and Controlling the Structures of Six‐Coordinate Copper(II) Centers: When Is a Compression Really a Compression?
No full textMix and Match – Controlling the Functionality of Spin-Crossover Materials Through Solid Solutions and Molecular Alloys
No full textThe influence of dopant molecules on the structure and functionality of spin-crossover (SCO) materials is surveyed. Two aspects of the topic are well established. Firstly, isomorphous inert metal ion dopants in SCO lattices are a useful probe of the energetics of SCO processes. Secondly, molecular alloys of iron(II)/triazole coordination polymers containing mixtures of ligands were used to tune their spin-transitions towards room temperature. More recent examples of these and related materials are discussed that reveal new insights into these questions. Complexes which are not isomorphous can also be co-crystallised, either as solid solutions of the precursor molecules or as a random distribution of homo- and hetero-leptic centres in a molecular alloy. This could be a powerful method to manipulate SCO functionality. Published molecular alloys show different SCO behaviours, which may or may not include allosteric switching of their chemically distinct metal sites
ChemInform Abstract: Recent Advances in the Synthesis and Applications of 2,6‐Dipyrazolylpyridine Derivatives and Their Complexes
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The Spin‐States and Spin‐Transitions of Mononuclear Iron(II) Complexes of Nitrogen Donor Ligands
No full textUsing one spin-transition to trigger another in solid solutions of two different spin-crossover complexes
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