Eun Hye Cha
Department of Chemistry, University of Ulsan
Self-Assembly of Chiral Molecular PolygonsWenbin Lin, J. Am. Chem. Soc., 2003, 125 (27), 8084–8085
Designed Self-Assembly of Molecular Necklaces Using Host-Stabilized Charge-Transfer Interactions
Kimoon Kim , J. Am. Chem. Soc., 2004, 126 (7), 1932–1933
Self-Assembly of Chiral Molecular Polygons
Wenbin Lin, J. Am. Chem. Soc., 2003, 125 (27), 8084–8085
Introduction Self-Assembly and Symmetry Considerations
Figure 1. “Molecular Library” of cyclic molecular polygons created via the systematic combination of ditopic building blocks with predetermined angles.
Peter J. Stang, Chem. Rev., 2000, 100 (3), 853–908
Figure 2. “Molecular Library” for the formation of 3D- assemblies from ditopic and tritopic subunits.
Experimental
Scheme 1.
• Each of the chiral molecular polygons was purified by silica gel column chromatography.
• Compounds have been characterized by 1H NMR spectrum, UV-vis, X-ray diffractionquality single crystal, and circular dichroism(CD) spectrum.
• [trans- (PEt3)2Pt(L)]n (n = 3-8, 1-6)
Result
Figure 3. 1H NMR spectra of 1−6 in CDCl3. Only the aromatic regions are shown.
1H NMR spectrum
Result
Figure 4. Stick and space-filling presentations of the energy-minimized structure of (S)-6.
X-ray diffraction-quality single crystal
Result
Figure 5. UV−vis spectra of 1−6 in acetonitrile. 0.8% of CH2Cl2 (v/v) was added to the solution of 4−6 to enhance the solubility.
UV−vis spectrum
236, 250nm – naphthyl π → π* transitions
288nm - acetylenic π → π* transition
335,360nm - acetylenic π → π* transitions
Result
Figure 6. CD spectra of 1−6 in acetonitrile. 0.8% of CH2Cl2 (v/v) was added to the solution of 4−6 to enhance the solubility.
Circular dichroism spectrum
260nm – naphthyl π → π* transition
360nm - acetylenic π → π* transition
Designed Self-Assembly of Molecular Necklaces Using Host-Stabilized
Charge-Transfer Interactions
Kimoon Kim , J. Am. Chem. Soc., 2004, 126 (7), 1932–1933
Scheme 2.
Experimental
Result
Figure 7. 1H NMR spectra of 1 in D2O (a) before and (b) after addition of 1 equiv of CB[8] (♦) at 25 °C.
1H NMR spectra
Result
Figure 8. Energy-minimized structure of molecular necklace 2 shown in stick and space-filling models. Hydrogen atoms in CB[8] are omitted.
X-ray diffraction-quality single crystal
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Incorporation of 2,6-Di(4,4’-dipyridyl)-9-thiabicyclo[3.3.1]nonane into Discrete
2D Supramolecules via Coordination-Driven Self-Assembly
Na-Ra Han
Advanced instrumental analysis lab
Reference•Seidel, S. R.; Stang, P. J. Acc. Chem. Res. ”High-Symmetry Coordination Cages via Self-Assembly” 2002, 35, 972-983.•Stang, P. J.; Persky, N. E.; Manna, J. J. Am. Chem. Soc. ”Molecular Architecture via Coordination: Self-Assembly of Nanoscale Platinum Containing Molecular Hexagons” 1997, 119, 4777-4778 .
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Introduction • The synthesis and characterization of three new supramolecular complexes 6-8 (a rhomboid and two
hexagons) via coordination-driven self-assembly are reported in excellent yields (>90%).
• These assemblies have 2,6-di(4,4’-dipyridyl)-9-thiabicyclo[3.3.1]nonane 2 as the bridging tecton.
• All assemblies were characterized by multinuclear NMR (1H and 31P), and elemental analysis.
• The design and synthesis of transition-metal-containing discrete nanoscopic structures via coordination-driven selfassembly is a very popular methodology often utilized in supramolecular chemistry.
• Several two-dimensional and three-dimensional supramolecular structures with well-defined shapes have been synthesized with potential applications in host-guest chemistry, catalysis, and chemical sensing.
• As far as two-dimensional macrocyclic structures are concerned, there are numerous examples of smaller polygons, such as triangles, rectangles, and squares.
• In comparison, there are fewer examples of larger polygons such as pentagons and hexagons.
• Hexagonal structures are especially interesting because they are one of the most common patterns found in nature.
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Experomental
SCHEME 1. Self-Assembly of 2 with Platinum Acceptors 3-5
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Result
Figure 2. A) 1H and B) 31P NMR spectra of Rhomboid 6 in Acetone-d6 / D2O: 5/1
Result
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Result
Figure .3 A) 1H and B) 31P NMR spectra of Hexagon 7 in Acetone-d6
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Result
Figure 4. A) 1H and B) 31P NMR spectra of Hexagon 8 in Acetone-d6 / CD2Cl2 : 1/1
SELF-ASSEMBLY OF THREE-DIMENSIONAL M3L2 CAGES VIA A NEW FLEXIBLE
ORGANOMETALLIC CLIP.
Organic Synthesis Lab.
20095149Young-ho Song
Hai-Bo Yang, Koushik Ghosh, Neeladri Das, and Peter J. Stang*
Department of Chemistry, UniVersity of Utah, 315 South 1400 East, RM 2020,Salt Lake City, Utah 84112
Org. Lett., 2006, 8 (18), pp 3991–3994
Typical iridovirus Icosahedral
Dodecahedron
Three-dimensional(3D) architectures
M3L2-type cageSimplest construction
Coordination-driven self-assembly has proven to be a highly effective approach.
CavitiesPotential applications in host-guest chemistry and catalysis
Trigonal bipyramidal structure
Reversibly encapsulate a molecule of C60
Ikeda, A.; Yoshimura, M.; Udzu, H.; Fukuhara, C.; Shinkai, S. J.Am. Chem. Soc. 1999, 121, 4296-4297.
Efficient unit into highly symmetric trigonal prismatic cages
Small sizeIt is important to design and synthesize a new molecular clip with a larger Pt-Pt distance .
Kuehl, C. J.; Huang, S. D.; Stang, P. J. J. Am. Chem. Soc. 2001, 123, 9634-9641.
Diethynylbenzene unit
Significant variation in physical properties Acetylene unit
Very useful tecton
Expectation of new cavityThe presence of multiple diethynylbenzene units may provide these 3D cages with new and interesting electronic and photonic properties.
Facile self-assembly of three-dimensional M3L2 cages via the flexible organometallic clip 7
31P NMR spectra of 7 in CD2Cl2
31P NMR spectra of 9a in CD2Cl2
31P NMR spectra of 9b in CD2Cl2
Planar tripod donors 10a and 10b
31P NMR spectra of 7 in CD2Cl2
31P NMR spectra of 11a in CD2Cl2
31P NMR spectra of 11b in CD2Cl2
Larger size of molecular clip 7
Flexible nature of clip 7
The structure of these 3D cages which possess large cavities was established by multinuclear NMR and ESI/MS spectral data along with elemental analysis.
Design of clip 7
Design of supramolecular cages 9a, 9b, 11a, and 11b based on a flexble clip 7
Construction of Coordination-Driven Self-Assembled [5 + 5] Pentagons Using
Metal-Carbonyl Dipyridine Ligands
Liang Zhao,*,† Koushik Ghosh,† Yaorong Zheng,† Matthew M. Lyndon,‡ Taufika Islam Williams,‡ and Peter J. Stang*,†
Inorganic Chemistry, Vol.48, No.13, 2009, 5590–5592
•Seong Min, Oh
•Undergraduate fourth
The coordination-driven self-assembly of two metal carbonylcluster-coordinated dipyridyl donors, (4C5H4N)2CtCCo2(CO)6 (1) and (4-C5H4N)2CtCMo2Cp2(CO)4 (2), with a linear
diplatinum(II) acceptor ligand was investigated.
Acetylene units (C C) are extensively incorporated into many donor and acceptor building blocks because of their rigid linear conformation. In view of the ready reactivity of a wide range of metal-carbonyl cluster complexes with acetylene moieties, we envisioned that the steric bulk of a metal-carbonyl cluster species adhered to the acetylene moiety may be used as a control factor to adjust the bonding angle of the building block in order to exclusively form a pentagonal self-assembly.
Two charge states at m/z 2040.1 and 1310.3 corresponding to [pentagon - 4CF3SO3]4+ and [pentagon - 6CF3SO3]6+, respectively, were observed and were in good agreement with their theoretical isotopic distributions. The isotopically wellresolved mass peak at m/z 1952.8, resulting from [hexagon - 5CF3SO3]5+, was found in the MS spectrum as well.(Figure 1 (a))
The ESI-TOF-MS spectrum of 5 displayed four peaks corresponding to four charge states of the [5+5] pentagon, including [M-3CF3SO3]3+ (m/z 3016.6), [M-4CF3SO3]4+(m/z 2225.0), [M-5CF3SO3]5+(m/z 1750.2), overlapping with the 1+fragment), and [M - 6CF3SO3]6+ (m/z1433.5)
(Figure 1 (b))
The modeled suprastructures show that the linear acceptor units in the hexagonal structure must distort away from a 180° orientation in order to fit the complementarity requirement of a [6 + 6] hexagon, whereas the acceptors retain their 180° geometry in themodeled [5+5] pentagonal structure
It have successfully prepared a [5 + 5] supramolecular pentagon by the self-assembly of a molybdenum-carbonyl cluster dipyridyl donor ligand (2) with a linear diplatinum(II) acceptor (3)
The Synthesis of New 60Organometallic Subunits and
Self-Assembly of Three-Dimensional M3L2 Trigonal-Bipyramidal
Cages
J. Org. Chem, Vol. 71, No. 25, 2006 pp.9464-9469
Hai-Bo Yang,* Koushik Ghosh, Atta M. Arif, and Peter J. Stang*
Department of Chemistry, UniVersity of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112
20071198Da-Ye Shin
The design and synthesis of three-dimensional cagesvia coordination-driven self-assembly
M3L2-type cages
Leininger, S.; Stang, P. J.; Huang, S. Organometallics 1998, 17,3981-3987.
SimiilarFigure
FIGURE 1. ORTEP diagram of 60° di-Pt(II) diiodide complex 5.
FIGURE 2. ORTEP diagram of 60° di-Pt(II) diiodide complex 10.
A similarphenomenon has been discussed in the
case of the anthracenebased“clip”.
SCHEME 3. Self-Assembly of Supramolecular TBP Cages
31P NMR spectra of M3L2 TBP cage 15 inDichloromethane-d2 /Acetone-d6: 7/1
31P NMR spectra of M3L2 TBP cage 14 inDichloromethane-d2 /Acetone-d6: 7/1
31P NMR spectra of M3L2 TBP cage 13 inAcetone-d6/D2O: 1/1
(A)
(B)
(C)
All three TBP cages are characterized with multinuclear NMR and electrospray ionization mass spectrometry (ESI-MS) along with element analysis.
Design of supramolecular cages
M3L2-type cages
