Self-Assembly of Chiral Molecular Polygons: A Designed Approach

1. Self-Assembly of Chiral Molecular Polygons Wenbin 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 Eun Hye Cha Department of Chemistry, University of Ulsan

2. Self-Assembly of Chiral Molecular Polygons Wenbin Lin, J. Am. Chem. Soc., 2003, 125 (27), 8084–8085

3. 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. Figure 2. “Molecular Library” for the formation of 3D- assemblies from ditopic and tritopic subunits. Peter J. Stang, Chem. Rev., 2000, 100 (3), 853–908

4. Experimental • [trans- (PEt3)2Pt(L)]n (n = 3-8, 1-6) • 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. Scheme 1.

5. Result 1H NMR spectrum Figure 3. 1H NMR spectra of 1−6 in CDCl3. Only the aromatic regions are shown.

6. Result X-ray diffraction-quality single crystal Figure 4. Stick and space-filling presentations of the energy-minimized structure of (S)-6.

7. Result UV−vis spectrum 236, 250nm – naphthyl π → π* transitions 288nm - acetylenic π → π* transition 335,360nm - acetylenic π → π* transitions 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.

8. Result Circular dichroism spectrum 260nm – naphthyl π → π* transition 360nm - acetylenic π → π* transition 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.

9. Designed Self-Assembly of Molecular Necklaces Using Host-Stabilized Charge-Transfer Interactions Kimoon Kim , J. Am. Chem. Soc., 2004, 126 (7), 1932–1933

10. Experimental Scheme 2.

11. Result 1H NMR spectra Figure 7. 1H NMR spectra of 1 in D2O (a) before and (b) after addition of 1 equiv of CB[8] (♦) at 25 °C.

12. Result X-ray diffraction-quality single crystal Figure 8. Energy-minimized structure of molecular necklace 2 shown in stick and space-filling models. Hydrogen atoms in CB[8] are omitted.

13. 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 .

14. 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.

15. Experomental SCHEME 1. Self-Assembly of 2 with Platinum Acceptors 3-5

16. Result Result Figure 2. A) 1H and B) 31P NMR spectra of Rhomboid 6 in Acetone-d6 / D2O: 5/1

17. Result Figure .3 A) 1H and B) 31P NMR spectra of Hexagon 7 in Acetone-d6

18. Result Figure 4. A) 1H and B) 31P NMR spectra of Hexagon 8 in Acetone-d6 / CD2Cl2 : 1/1

19. SELF-ASSEMBLY OF THREE-DIMENSIONAL M3L2 CAGES VIA A NEW FLEXIBLE ORGANOMETALLIC CLIP. 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 Organic SynthesisLab. 20095149 Young-ho Song

20. Introduction 3D structure Three-dimensional(3D) architectures Icosahedral Typical iridovirus Dodecahedron

21. Introduction 3D cage M3L2-type cage Simplest construction Coordination-driven self-assembly has proven to be a highly effective approach. Cavities Potential applications in host-guest chemistry and catalysis

22. Introduction Example of cage 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.

23. Introduction Example of clip Efficient unit into highly symmetric trigonal prismatic cages 5.6 Å Small size It 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.

24. Molecular“clip” (7) 14.45 Å Diethynylbenzene unit Very useful tecton Acetylene unit Significant variation in physical properties Expectation of new cavity The presence of multiple diethynylbenzene units may provide these 3D cages with new and interesting electronic and photonic properties.

25. Experimental

26. Self-Assembly 9a and 9b Facile self-assembly of three-dimensional M3L2 cages via the flexible organometallic clip 7

27. Self-Assembly Comparison size = +

28. Results & Discussion 9a and 9b 31P NMR spectra of 7 in CD2Cl2 2 + 3 31P NMR spectra of 9a in CD2Cl2 9a 2 + 3 31P NMR spectra of 9b in CD2Cl2 9b

29. Results & Discussion 9a and 9b

30. Self-Assembly 11a and 11b Planar tripod donors 10a and 10b

31. Results & Discussion 11a and 11b 31P NMR spectra of 7 in CD2Cl2 2 + 3 31P NMR spectra of 11a in CD2Cl2 9a + 3 2 31P NMR spectra of 11b in CD2Cl2 9b

32. Results & Discussion 11a and 11b

33. Conclusion Larger size of molecular clip 7 Design of clip 7 Flexible nature of clip 7 Design of supramolecular cages 9a, 9b, 11a, and 11b based on a flexble 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.

34. Construction of Coordination-Driven Self-Assembled [5 + 5] Pentagons UsingMetal-Carbonyl Dipyridine LigandsLiang 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

35. 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.

36. 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.

37. 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))

38. 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

39. 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)

40. The Synthesis of New 60° Organometallic Subunits andSelf-Assembly of Three-Dimensional M3L2 Trigonal-BipyramidalCages Hai-Bo Yang,* Koushik Ghosh, Atta M. Arif, and Peter J. Stang* J. Org. Chem, Vol. 71, No. 25, 2006 pp.9464-9469 Department of Chemistry, UniVersity of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112 20071198 Da-Ye Shin

41. Introduction M3L2-type cages The design and synthesis of three-dimensional cages via coordination-driven self-assembly

42. Experimental Leininger, S.; Stang, P. J.; Huang, S. Organometallics 1998, 17, 3981-3987.

43. Experimental

44. X-ray Structure Simiilar Figure A similar phenomenon has been discussed in the case of the anthracenebased “clip”. FIGURE 2. ORTEP diagram of 60° di-Pt(II) diiodide complex 10. FIGURE 1. ORTEP diagram of 60° di-Pt(II) diiodide complex 5.

45. Self-Assembly SCHEME 3. Self-Assembly of Supramolecular TBP Cages

46. Results & Discussion

47. Results & Discussion (A) 31P NMR spectra of M3L2 TBP cage 13 in Acetone-d6/D2O: 1/1 (B) 31P NMR spectra of M3L2 TBP cage 14 in Dichloromethane-d2 /Acetone-d6: 7/1 (C) 31P NMR spectra of M3L2 TBP cage 15 in Dichloromethane-d2 /Acetone-d6: 7/1

48. Results & Discussion

49. Conclusion Design of supramolecular cages M3L2-type cages All three TBP cages are characterized with multinuclear NMR and electrospray ionization mass spectrometry (ESI-MS) along with element analysis.