examining the construction of potential coordination polymers … · 2018-09-09 · coordination...
TRANSCRIPT
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Examining the Construction of Potential Coordination Polymers
with Aromatic N-oxides of
Mercury(II)
Michael Tran, Will Lynch and Cliff Padgett
Department of Chemistry and Physics
Armstrong Student Scholars Symposium
April 21, 2016
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Coordination Polymers & N-oxides
• Supramolecular chemistry is a growing field of
interest
• Unique topologies and potential applications
• Applications such as gas storage, ion exchange
processes for remediation, heterogeneous
catalysis
• N-oxides: Variability of construction allows for
multiple binding modes and investigation of steric
and electronic effects
• Solid State Sciences, 2011, 13, 1692-1700.
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Example Binding Modes of Aromatic N-oxides
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Single Crystal X-ray Crystallography
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General Synthetic Scheme
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Pyridine N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.673
Hg1 – Br1 2.445
Hg1 – Br2 2.459
Bond Angle (°)
Br1 – Hg1 – Br2 159.38
Br1 – Hg1 – O1 96.62
Br2 – Hg1 – O1 89.10
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Pyridine N-oxide / HgBr2
Coordination Polymer
Zig-Zag 1-D Polymer with N-oxide Bridges
2 terminal bromides per Hg
Hg:N-oxide 1:1
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3-Picoline N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.702
Hg1 – Br1 2.435
Hg1 – Br2 2.448
Bond Angle (°)
Br1 – Hg1 – Br2 160.05
Br1 – Hg1 – O1 98.41
Br2 – Hg1 – O1 88.58
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3-Picoline N-oxide / HgBr2
Coordination Polymer
Zig-Zag 1-D Polymer with N-oxide Bridges
2 terminal bromides per Hg
Hg:N-oxide 1:1
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4-Picoline N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.542
Hg1 – Br1 2.462
Hg1 – Br2 2.449
Bond Angle (°)
Br1 – Hg1 – Br2 163.88
Br1 – Hg1 – O1 92.73
Br2 – Hg1 – O1 95.81
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4-Picoline N-oxide / HgBr2
Coordination Polymer
Braided Polymer with Br- and N-oxide Bridges
1 bridging bromide, 1 terminal bromide per Hg
Hg:N-oxide 1:1
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4-Methoxypyridine N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.531
Hg1 – Br1 2.462
Hg1 – Br2 2.445
Bond Angle (°)
Br1 – Hg1 – Br2 167.66
Br1 – Hg1 – O1 85.95
Br2 – Hg1 – O1 94.82
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4-Methoxypyridine N-oxide / HgBr2
Coordination Polymer
Braided Polymer with Br- and N-oxide Bridges
1 bridging bromide, 1 terminal bromide per Hg
Hg:N-oxide 1:1
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Quinoline N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.408
Hg1 – Br1 2.450
Hg1 – Br2 2.460
Bond Angle (°)
Br1 – Hg1 – Br2 157.20
Br1 – Hg1 – O1 101.43
Br2 – Hg1 – O1 101.23
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Quinoline N-oxide / HgBr2
Coordination Polymer
Braided Polymer with Alternating Br- and N-oxide Bridges
1 bridging bromide, 1 terminal bromide per Hg
Hg:N-oxide 1:1
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Isoquinoline N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.768
Hg1 – Br1 2.438
Hg1 – Br2 2.447
Bond Angle (°)
Br1 – Hg1 – Br2 160.11
Br1 – Hg1 – O1 96.56
Br2 – Hg1 – O1 90.01
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Isoquinoline N-oxide / HgBr2
Coordination Polymer
1-D Polymer with N-oxide Bridges
2 terminal bromides
Hg:N-oxide 1:1
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6-Methoxyquinoline N-oxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.630
Hg2 – O1 2.491
Hg1 – Br1 2.438
Hg1 – Br2 2.429
Hg2 – Br3 2.455
Bond Angle (°)
Br1 – Hg1 – Br2 178.35
Br1 – Hg1 – O1 88.27
Br2 – Hg1 – O1 93.36
Br3 – Hg2 – O1 96.09
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6-Methoxyquinoline N-oxide / HgBr2
Coordination Polymer
Double Braided Polymer with Br- and N-oxide Bridges
1 bridging bromide, 1 terminal bromide per Hg
Hg:N-oxide 2:1
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2,2’-Dypyridyl N,N’-dioxide / HgBr2
Bond Length (Å)
Hg1 – O1 2.472
Hg1 – O2 2.459
Hg1 – Br1 2.474
Hg1 – Br2 2.474
Bond Angle (°)
Br1 – Hg1 – Br2 158.30
Br1 – Hg1 – O1 104.97
O1 – Hg1 – O2 71.90
Br2 – Hg1 – O2 99.95
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2,2’-Dypyridyl N,N’-dioxide / HgBr2
Monomer Bidentate Chelate
Monomer with π-π StackingHg:N-oxide 1:1
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2,2’-Dypyridyl N,N’-dioxide / HgCl2
Bond Length (Å)
Hg1 – O1 2.458
Hg1 – O2 2.472
Hg1 – Cl1 2.334
Hg1 – Cl2 2.339
Bond Angle (°)
Cl1 – Hg1 – Cl2 161.45
Cl1 – Hg1 – O1 103.63
O1 – Hg1 – O2 70.97
Cl2 – Hg1 – O2 99.02
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2,2’-Dypyridyl N,N’-dioxide / HgCl2Monomer Bidentate Chelate
Monomer with π-π StackingHg:N-oxide 1:1
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Data Summary
Compound Hg-O (Å)
Hg-Br (Å)
Br-Hg-Br (°) Hg : N-oxide
Description
PNO 2.67 2.45 160 1:1 Zig-Zag N-oxide Bridge
3MePNO 2.70 2.44 160 1:1 Zig-Zag N-oxide Bridge
4MePNO 2.54 2.46 164 1:1 Braided Br- & N-oxide
Bridges
4MeOPNO 2.51 2.46 168 1:1 Braided Br- & N-oxide
Bridges
QNO 2.41 2.45 157 1:1 Braided Br- & N-oxide
Bridges
iQNO 2.77 2.44 160 1:1 Zig-Zag N-oxide Bridge
6MeOQNO 2.63,
2.49
2.44 178 2:1 Double Braided Br- & N-
oxide Bridges
2,2’-DPNO 2.46 2.47 158 1:1 Chelate Monomer
2,2’-DPNO 2.46 2.33* 161 1:1 Chelate Monomer
* Chloride
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Conclusions
•N-oxide monomeric ligands are effective ligands
for forming O-Hg-O coordination polymers
•Bromide is capable of serving as both bridge and
terminal ligands in these systems
•N-oxide ligands with chelate ligand
environments for monomers
• For PNO substituted N-oxides, the Hg-O bond
length follows a general Hammett trend
•The bulkier the ligand the more “sophisticated” the
polymeric chain
•The polymers form with a general organic (π-π)
stacking layer and a inorganic layer