期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 21, 页码 6813-6821出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b02445
关键词
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资金
- European Union [642192]
- UK Engineering and Physical Sciences Research Council (EPSRC)
- Michelin SCA
- University of Cambridge
- Corpus Christi College, Cambridge
- Gates Cambridge Trust
- Cambridge Commonwealth, European and International Trust
- Engineering and Physical Sciences Research Council [EP/M008258/1, EP/K039520/1] Funding Source: researchfish
- EPSRC [EP/M008258/1, EP/K039520/1] Funding Source: UKRI
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 S-positions resulted in stereoselective formation of the iron(I1) 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 sigma(+)(p) 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.
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