Skip to main content

The Template-Directed Synthesis of a Fully Conjugated 14-Porphyrin Nanoball

  • Chapter
  • First Online:
Electronic Communication in Heterometallated Porphyrin Oligomers

Part of the book series: Springer Theses ((Springer Theses))

  • 234 Accesses

Abstract

The preparation of conjugated organic systems with strong π-orbital overlap between the molecular components is both challenging and laborious. This chapter describes the template-directed synthesis and characterisation of a π-conjugated 14-porphyrin nanoball. The bicyclic structure consists of a 6- and 10-porphyrin nanoring intersecting at two points. UV-Vis-NIR titrations were performed to investigate the binding behaviour of the templates inside the cavity of the ball. In addition, photoluminescence (PL) upconversion spectroscopy revealed strong coupling between the two rings. By removing the templates, the flexibility in the system increases which results in a decrease in the PL anisotropy. This indicates that excitations may migrate between the two ring components of the nanoball.

Parts of this chapter have been reproduced from:

Template-directed synthesis of a conjugated zinc porphyrin nanoball.

J. Cremers, R. Haver, M. Rickhaus, J. Q. Gong, L. Favereau, M. D. Peeks, T. D. W. Claridge, L. M Herz, H. L Anderson, J. Am. Chem. Soc. 2018, 16, 5352–5355 (Reprinted (adapted) with permission from J. Am. Chem. Soc. 2018, 16, 5352–5355. Copyright 2019 American Chemical Society. https://pubs.acs.org/doi/10.1021/jacs.8b02552).

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 109.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Richert S, Cremers J, Kuprov I, Peeks MD, Anderson HL, Timmel CR (2017) Constructive quantum interference in a bis-copper six-porphyrin nanoring. Nat Commun 8:14842

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  2. Peeks MD, Claridge TDW, Anderson HL (2017) Aromatic and antiaromatic ring currents in a molecular nanoring. Nature 541:200

    Article  CAS  PubMed  Google Scholar 

  3. Hoffmann M, Kärnbratt J, Chang M-H, Herz LM, Albinsson B, Anderson HL (2008) Enhanced π conjugation around a porphyrin[6] nanoring. Angew Chem Int Ed 47:4993

    Article  CAS  Google Scholar 

  4. O’Sullivan MC, Sprafke JK, Kondratuk DV, Rinfray C, Claridge TD, Saywell A, Blunt MO, O’Shea JN, Beton PH, Malfois M, Anderson HL (2011) Vernier templating and synthesis of a 12-porphyrin nano-ring. Nature 469:72

    Article  PubMed  CAS  Google Scholar 

  5. Hoffmann M, Wilson CJ, Odell B, Anderson HL (2007) Template‐directed synthesis of a π‐conjugated porphyrin nanoring. Angew Chem Int Ed 46:3122

    Article  CAS  Google Scholar 

  6. Kondratuk DV, Perdigao LMA, O’Sullivan MC, Svatek S, Smith G, O’Shea JN, Beton PH, Anderson HL (2012) Two vernier‐templated routes to a 24‐porphyrin nanoring. Angew Chem Int Ed 51:6696

    Article  CAS  Google Scholar 

  7. Kondratuk DV, Perdigão LMA, Esmail AMS, O’Shea JN, Beton PH, Anderson HL (2015) Supramolecular nesting of cyclic polymers. Nat Chem 7:317

    Article  CAS  PubMed  Google Scholar 

  8. Neuhaus P, Cnossen A, Gong JQ, Herz LM, Anderson HL (2015) A molecular nanotube with three‐dimensional π‐conjugation. Angew Chem Int Ed 54:7344

    Article  CAS  Google Scholar 

  9. Favereau L, Cnossen A, Kelber JB, Gong JQ, Oetterli RM, Cremers J, Herz LM, Anderson HL (2015) Six-coordinate zinc porphyrins for template-directed synthesis of spiro-fused nanorings. J Am Chem Soc 137:14256

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Kroto HW, Heath JR, O’Brien SC, Curl RF, Smalley RE (1985) C60: buckminsterfullerene. Nature 318:162

    Article  CAS  Google Scholar 

  11. Scott LT, Boorum MM, McMahon BJ, Hagen S, Mack J, Blank J, Wegner H, de Meijere A (2002) A rational chemical synthesis of C60. Science 295:1500

    Article  CAS  PubMed  Google Scholar 

  12. Kabdulov M, Jansen M, Amsharov KY (2013) Bottom‐up C60 fullerene construction from a fluorinated C60H21F9 precursor by laser‐induced tandem cyclization. Chem Eur J 19:17262

    Article  CAS  PubMed  Google Scholar 

  13. Greisch J-F, Amsharov KY, Weippert J, Weis P, Böttcher A, Kappes MM (2016) From planar to cage in 15 easy steps: resolving the C60H21F9 → C60 transformation by ion mobility mass spectrometry. J Am Chem Soc 138:11254

    Article  CAS  PubMed  Google Scholar 

  14. Matsui K, Segawa Y, Namikawa T, Kamada K, Itami K (2013) Synthesis and properties of all-benzene carbon nanocages: a junction unit of branched carbon nanotubes. Chem Sci 4:84

    Article  CAS  Google Scholar 

  15. Kayahara E, Iwamoto T, Takaya H, Suzuki T, Fujitsuka M, Majima T, Yasuda N, Matsuyama N, Seki S, Yamago S (2013) Synthesis and physical properties of a ball-like three-dimensional π-conjugated molecule. Nat Commun 4:2694

    Article  PubMed  CAS  Google Scholar 

  16. Matsui K, Segawa Y, Itami K (2014) All-benzene carbon nanocages: size-selective synthesis, photophysical properties, and crystal structure. J Am Chem Soc 136:16452

    Article  CAS  PubMed  Google Scholar 

  17. Ikemoto K, Kobayashi R, Sato S, Isobe H (2017) Synthesis and bowl‐in‐bowl assembly of a geodesic phenylene bowl. Angew Chem Int Ed 56:6511

    Article  CAS  Google Scholar 

  18. Gutzler R, Perepichka DF (2013) π-electron conjugation in two dimensions. J Am Chem Soc 135:16585

    Article  CAS  PubMed  Google Scholar 

  19. Peeks MD, Tait CE, Neuhaus P, Fischer GM, Hoffmann M, Haver R, Cnossen A, Harmer JR, Timmel CR, Anderson HL (2017) Electronic delocalization in the radical cations of porphyrin oligomer molecular wires. J Am Chem Soc 139:10461

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. Ball M, Zhong Y, Fowler B, Zhang B, Li P, Etkin G, Paley DW, Decatur J, Dalsania AK, Li H, Xiao S, Ng F, Steigerwald ML, Nuckolls C (2016) Macrocyclization in the design of organic n-type electronic materials. J Am Chem Soc 138:12861

    Article  CAS  PubMed  Google Scholar 

  21. Zhang G, Mastalerz M (1934) Organic cage compounds—from shape-persistency to function. Chem Soc Rev 2014:43

    Google Scholar 

  22. Hasell T, Cooper AI (2016) Porous organic cages: soluble, modular and molecular pores. Nat Rev Mater 1:16053

    Article  CAS  Google Scholar 

  23. Olenyuk B, Levin MD, Whiteford JA, Shield JE, Stang PJ (1999) Self-assembly of nanoscopic dodecahedra from 50 predesigned components. J Am Chem Soc 121:10434

    Article  CAS  Google Scholar 

  24. Sun Q-F, Iwasa J, Ogawa D, Ishido Y, Sato S, Ozeki T, Sei Y, Yamaguchi K, Fujita M (2010) Self-assembled M24L48 polyhedra and their sharp structural switch upon subtle ligand variation. Science 328:1144

    Article  CAS  PubMed  Google Scholar 

  25. Zarra S, Wood DM, Roberts DA, Nitschke JR (2015) Molecular containers in complex chemical systems. Chem Soc Rev 44:419

    Article  CAS  PubMed  Google Scholar 

  26. Zhang G, Presly O, White F, Oppel IM, Mastalerz M (2014) A shape‐persistent quadruply interlocked giant cage catenane with two distinct pores in the solid state. Angew Chem Int Ed 53:5126

    CAS  Google Scholar 

  27. Rue NM, Sun J, Warmuth R (2011) Polyimine container molecules and nanocapsules. Isr J Chem 51:743

    Article  CAS  Google Scholar 

  28. Zhu B, Chen H, Lin W, Ye Y, Wu J, Li S (2014) Template-directed synthesis of flexible porphyrin nanocage and nanorings via one-step olefin metathesis. J Am Chem Soc 136:15126

    Article  CAS  PubMed  Google Scholar 

  29. Zhang C, Wang Q, Long H, Zhang W (2011) A highly C70 selective shape-persistent rectangular prism constructed through one-step alkyne metathesis. J Am Chem Soc 133:20995

    Article  CAS  PubMed  Google Scholar 

  30. Lee S, Yang A, Moneypenny TP, Moore JS (2016) Kinetically trapped tetrahedral cages via alkyne metathesis. J Am Chem Soc 138:2182

    Article  CAS  PubMed  Google Scholar 

  31. Anderson S, Anderson HL, Sanders JKM (1993) Expanding roles for templates in synthesis. Acc Chem Res 26:469

    Article  CAS  Google Scholar 

  32. Wasielewski MR (2009) Self-assembly strategies for integrating light harvesting and charge separation in artificial photosynthetic systems. Acc Chem Res 42:1910

    Google Scholar 

  33. Aratani N, Kim D, Osuka A (2009) Discrete cyclic porphyrin arrays as artificial light-harvesting antenna. Acc Chem Res 42:1922

    Google Scholar 

  34. Parkinson P, Kondratuk DV, Menelaou C, Gong JQ, Anderson HL, Herz LM (2014) Chromophores in molecular nanorings: when is a ring a ring?. J Phys Chem Lett 5:4356

    Article  CAS  PubMed  Google Scholar 

  35. Screen TEO, Lawton KB, Wilson GS, Dolney N, Ispasoiu R, Goodson T III, Martin SJ, Bradley DDC, Anderson HL (2001) Synthesis and third order nonlinear optics of a new soluble conjugated porphyrin polymer. J Mater Chem 11:312

    Article  CAS  Google Scholar 

  36. Scott Wilson G, Anderson HL (1999) A conjugated triple strand porphyrin array. Chem Commun 1539

    Google Scholar 

  37. Hogben HJ, Sprafke JK, Hoffmann M, Pawlicki M, Anderson HL (2011) Stepwise effective molarities in porphyrin oligomer complexes: preorganization results in exceptionally strong chelate cooperativity. J Am Chem Soc 133:20962

    Article  CAS  PubMed  Google Scholar 

  38. Cremers J, Richert S, Kondratuk DV, Claridge TDW, Timmel CR, Anderson HL (2016) Nanorings with copper(II) and zinc(II) centers: forcing copper porphyrins to bind axial ligands in heterometallated oligomers. Chem Sci 7:6961

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Liu P, Neuhaus P, Kondratuk DV, Balaban TS, Anderson HL (2014) Cyclodextrin‐templated porphyrin nanorings. Angew Chem Int Ed 53:7770

    Article  CAS  Google Scholar 

  40. Robinson PT, Pham TN, Uhrı́n D (2004) In phase selective excitation of overlapping multiplets by gradient-enhanced chemical shift selective filters. J Magn Reson 170:97

    Article  CAS  PubMed  Google Scholar 

  41. Duncan SJ, Lewis R, Bernstein MA, Sandor P (2007) Selective excitation of overlapping multiplets; the application of doubly selective and chemical shift filter experiments to complex NMR spectra. Magn Reson Chem 45:283

    Article  CAS  PubMed  Google Scholar 

  42. Rousseaux SAL, Gong JQ, Haver R, Odell B, Claridge TDW, Herz LM, Anderson HL (2015) Self-assembly of Russian doll concentric porphyrin nanorings. J Am Chem Soc 137:12713

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  43. Liu S, Kondratuk DV, Rousseaux SAL, Gil-Ramírez G, O’Sullivan MC, Cremers J, Claridge TDW, Anderson HL (2015) Caterpillar track complexes in template‐directed synthesis and correlated molecular motion. Angew Chem Int Ed 54:5355

    Article  CAS  Google Scholar 

  44. Gong JQ, Parkinson P, Kondratuk DV, Gil-Ramírez G, Anderson HL, Herz LM (2015) Structure-directed exciton dynamics in templated molecular nanorings. J Phys Chem C 119:6414

    Article  CAS  Google Scholar 

  45. Yong C-K, Parkinson P, Kondratuk DV, Chen W-H, Stannard A, Summerfield A, Sprafke JK, O’Sullivan MC, Beton PH, Anderson HL, Herz LM (2015) Ultrafast delocalization of excitation in synthetic light-harvesting nanorings. Chem Sci 6:181

    Article  CAS  PubMed  Google Scholar 

  46. Sprafke JK, Kondratuk DV, Wykes M, Thompson AL, Hoffmann M, Drevinskas R, Chen W-H, Yong CK, Kärnbratt J, Bullock JE, Malfois M, Wasielewski MR, Albinsson B, Herz LM, Zigmantas D, Beljonne D, Anderson HL (2011) Belt-shaped π-systems: relating geometry to electronic structure in a six-porphyrin nanoring. J Am Chem Soc 133:17262

    Article  CAS  PubMed  Google Scholar 

  47. Gong JQ, Favereau L, Anderson HL, Herz LM (2016) Breaking the symmetry in molecular nanorings. J Phys Chem Lett 7:332

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  48. Fedorov A, Berberan-Santos MN, Lefèvre J-P, Valeur B (1997) Picosecond time-resolved and steady-state studies of the polarization of the fluorescence of C60 and C70. Chem Phys Lett 267:467

    Article  CAS  Google Scholar 

  49. Kerisit N, Toupet L, Larini P, Perrin L, Guillemin J-C, Trolez Y (2015) Straightforward synthesis of 5‐bromopenta‐2,4‐diynenitrile and its reactivity towards terminal alkynes: a direct access to diene and benzofulvene scaffolds. Chem Eur J 21:6042

    Article  CAS  PubMed  Google Scholar 

  50. Scott Wilson G, Anderson H (1996) A conjugated triple strand porphyrin array. Chem Commun 16:1539

    Google Scholar 

  51. Benson SW (1958) Statistical factors in the correlation of rate constants and equilibrium constants. J Am Chem Soc 80:5151

    Article  CAS  Google Scholar 

  52. Ercolani G, Piguet C, Borkovec M, Hamacek J (2007) Symmetry numbers and statistical factors in self-assembly and multivalency. J Phys Chem B 111:12195

    Article  CAS  PubMed  Google Scholar 

  53. Hunter CA, Anderson HL (2009) What is cooperativity?. Angew Chem Int Ed 48:7488

    Article  CAS  Google Scholar 

  54. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ (2013) Gaussian 09. Revision D.01. Software, Wallingford CT

    Google Scholar 

  55. Becke AD (1993) Density‐functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648

    Article  CAS  Google Scholar 

  56. Ditchfield R, Hehre WJ, Pople JA (1971) Self‐consistent molecular‐orbital methods. IX. An extended Gaussian‐type basis for molecular‐orbital studies of organic molecules. J Chem Phys 54:724

    Article  CAS  Google Scholar 

  57. Hehre WJ, Ditchfield R, Pople JA (1972) Self—consistent molecular orbital methods. XII. Further extensions of Gaussian—type basis sets for use in molecular orbital studies of organic molecules. J Chem Phys 56:2257

    Article  CAS  Google Scholar 

  58. Hariharan PC, Pople JA (1973) The influence of polarization functions on molecular orbital hydrogenation energies. Theor Chem Acc 28:213

    Article  CAS  Google Scholar 

  59. Rassolov VA, Pople JA, Ratner MA, Windus TL (1998) 6-31G* basis set for atoms K through Zn. J Chem Phys 109:1223

    Article  CAS  Google Scholar 

  60. Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104

    Article  PubMed  CAS  Google Scholar 

  61. Valeur P, Berberan-Santos MN (2012) Molecular fluorescence: principles and applications. Wiley, New York

    Book  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Jonathan Cremers .

Rights and permissions

Reprints and permissions

Copyright information

© 2020 Springer Nature Switzerland AG

About this chapter

Check for updates. Verify currency and authenticity via CrossMark

Cite this chapter

Cremers, J. (2020). The Template-Directed Synthesis of a Fully Conjugated 14-Porphyrin Nanoball. In: Electronic Communication in Heterometallated Porphyrin Oligomers. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-39101-0_5

Download citation

Publish with us

Policies and ethics