Perfluorinated ligands induce meridional metal stereochemistry to generate M8L12, M10L15, and M12L18 prisms

Article abstract of DOI:10.1021/jacs.6b02445

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 σ_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.

Full text of DOI:10.1021/jacs.6b02445

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Article
Perfluorinated ligands induce meridional metal
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12
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stereochemistry to generate ML, ML and ML prisms
Marion Kieffer, Ben S. Pilgrim, Tanya K Ronson, Derrick
A. Roberts, Mina Aleksanyan, and Jonathan R. Nitschke
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b02445 • Publication Date (Web): 04 May 2016
Downloaded from http://pubs.acs.org on May 4, 2016
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stry to generate M8L12, M10L15 and M12L18 prisms
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ACS Paragon Plus Environment

Page 5 of 20
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
(a)
Tetrahedron 3
(b)
Tetragonal prism 4a
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.30
0.25
0.20
0.15
0.10
0.05
Observed
Observed
Statistical
Statistical
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
0.0
22
20
18
16
14
12
10
8
0.00
22
20
18
16
14
12
10
8
0
1
2
3
4
5
6
0
1
2
3
4
5
6
7
8
9
10 11 12
Number of fluorinated ligands (N)
Number of fluorinated ligands (N)
(c)
(d)
E
= a N + C
E
= a N + C
rt
t
t
rp p p
6
6
a = 4.06 ê 0.448
a
= -2.72 ê 0.128
t
p
4
4
2
2
= 0.987
R
= 0.953
R
2
2
0
0
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 20
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ACS Paragon Plus Environment

Page 7 of 20
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 20
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AUTHOR INFORMATION
Corresponding Author
ACS Paragon Plus Environment

Page 9 of 20
Journal of the American Chemical Society
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Figure 1. Self-assembly of fac and mer mononuclear complexes 1 and 2. 1H NMR spectra (400 MHz, 298 K,
CD3CN) of the imine regions of 1 and 2. Self-assembly of tetrahedral 3 and tetragonal prismatic 4 from the
non-fluorinated C and tetrafluorinated D subcomponents respectively.
369x232mm (192 x 192 DPI)
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Figure 2. Views of the single crystal Xꢀray structure of 4a (a) showing the top and bottom rings linked by
axial ligands, with linkages between FeII centers (purple spheres) added in order to highlight the D4 point
symmetry; (b) showing the ligands in a spaceꢀfilling view down the central channel; (c) highlighting a pair of
mer vertices, with the three magnetically distinct environments shown in blue, red, and green; (d) showing
the placement of the ordered PF6− counterions above the ꢀC6F4ꢀ rings. In all views the nonꢀencapsulated
anions, solvent molecules and disorder are omitted for clarity.
564x565mm (192 x 192 DPI)
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Figure 3. ESI-MS of a mixture of preformed structures 3 and 4a in a 2:1 ratio after equilibration at 50 °C
for one week.
604x594mm (192 x 192 DPI)
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Figure 4. Proportion of each species observed for (a) tetrahedron 3 and (b) tetragonal prism 4a compared
to the binomial (statistical) distribution. Error bars represent the standard deviations of the amounts of each
congener measured between the different charge states observed in the ESIꢀMS. (c) and (d) provide plots of
the energy of each species relative to tetrahedron 3 in (c), containing only nonꢀfluorinated C residues, and
the tetragonal prism 4a in (d), containing only fluorinated D residues. Ert and Erp refer to the relative
energies between congeners respectively in the cases of the tetrahedral series and the prismatic series. α
represents the energetic destabilization per ligand exchanged.
393x262mm (192 x 192 DPI)
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Figure 5. ESI-MS of a mixture of (a) 4b and 5b and (b) 5a and 6a.
654x1034mm (192 x 192 DPI)
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Figure 6. Single crystal Xꢀray structure of 5c showing (a) the two pentagonal faces linked by axial ligands,
with connections between metal centers (purple spheres) added to highlight the C5h point symmetry; (b)
spacefilling view down the central channel; (c) side view showing the specific positions of the localized PF6−
counterions. In all views the nonꢀencapsulated anions, solvent molecules and disorder are omitted for
clarity.
793x261mm (192 x 192 DPI)
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Figure 7. (a) MM3-optimized molecular model of hexagonal prism 6h (R=H). Connections between metal
centers (purple spheres) have been added to highlight the D6 point symmetry; (b) spacefilling view down
the central channel. No anions were modeled.
327x594mm (192 x 192 DPI)
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Figure 8. Equilibria between 4 and 5 show a linear free energy relationship between log(K) and σp+
following the Hammett Equation. The error bars show standard deviations of log(K) over 5 runs.
593x594mm (192 x 192 DPI)
,
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793x393mm (192 x 192 DPI)
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