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Perfluorinated Ligands Induce Meridional Metal Stereochemistry to Generate M8L12, M10L15, and M12L18 Prisms.

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Pilgrim, Ben S 
Ronson, Tanya K 
Roberts, Derrick A 
Aleksanyan, Mina 


Meridional (mer) coordination promotes the generation of larger and lower-symmetry prismatic metallosupramolecular structures, in contrast with the facial (fac) coordination common to smaller and higher-symmetry polyhedra. Here, we describe a general route to the selective formation of large metallosupramolecular prisms that contain exclusively mer-coordinated metal vertices. The use of 2-formylpyridine subcomponents that contain perfluorophenylene substituents at their 5-positions resulted in stereoselective formation of the iron(II) complexes from these subcomponents. Only mer vertices were observed, as opposed to the statistical fac/mer mixture otherwise generated. This mer-selective self-assembly could be used to prepare tetragonal (M8L12), pentagonal (M10L15), and hexagonal (M12L18) prisms by taking advantage of the subtle selectivities imposed by the different anilines and counterions employed. The equilibrium between the tetragonal and pentagonal prism followed a linear free-energy relationship, with the ratio between structures correlating with the Hammett σp(+) parameter of the incorporated aniline. The contrasting preferences of the fluorinated and nonfluorinated ligands to generate prisms and tetrahedra, respectively, were quantified energetically, with the destabilization increasing linearly for each "incorrect ligand" incorporated into either structure.



0302 Inorganic Chemistry

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J Am Chem Soc

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American Chemical Society (ACS)
Engineering and Physical Sciences Research Council (EP/K039520/1)
Engineering and Physical Sciences Research Council (EP/M008258/1)
European Commission (642192)
This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 642192 and was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). The authors thank Diamond Light Source (UK) for synchrotron beamtime on I19 (MT8464 and MT11397), the Department of Chemistry NMR facility, University of Cambridge, and the EPSRC UK National Mass Spectrometry Facility at Swansea University. M.K. acknowledges the Cambridge Commonwealth, European and International Trust and the Frédéric Fontaine scholarship from Michelin SCA. B.S.P. acknowledges the Herchel Smith Research Fellowship from the University of Cambridge and a Fellowship from Corpus Christi College, Cambridge. D.A.R. acknowledges the Gates Cambridge Trust for Ph.D. funding.