CC BY-NC-ND 4.0 · Organic Materials 2020; 02(04): 300-305
DOI: 10.1055/s-0040-1718934
Focus Issue: Curved Organic π-Systems
Short Communication

A Theoretical Study on the Macrocyclic Strain of Zigzag Molecular Belts

a  MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China
,
a  MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China
,
b  Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China
,
a  MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China
› Institutsangaben
Funding Information We thank the National Science Foundation of China (grant No. 21732004 and 21821001) and Tsinghua University Initiative Scientific Research Program for financial support.


Abstract

Zigzag molecular belts have captured the imagination of scientists for over a half century because of their aesthetically appealing structures and tantalizing properties. One of the formidable challenges in synthesis is to circumvent the energy accumulated in the construction of strained structures. Reported herein is our theoretical study to quantify the molecular strain energies. A general exponential function equation E strain = a·n·e n/b was obtained to estimate strain energies of both conjugated and partially hydrogenated hydrocarbon belts and their heteroatom-embedded analogs. The deformation of aromatic rings from planarity was revealed to contribute dominantly to the high strain energies. The method enabled the convenient quantification of the energetics of aromatization processes from partially hydrogenated double-stranded macrocycles, and facilitated the design and optimization of practical routes to synthesize the long-awaited zigzag molecular belts.

Supporting Information

Supporting information for this article is available online at http://doi.org/10.1055/s-0040-1718934. It shows detailed calculation results.


Supporting Information

Primary Data



Publikationsverlauf

Eingereicht: 24. August 2020

Angenommen: 14. September 2020

Publikationsdatum:
22. November 2020 (online)

© 2020. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/).

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References and Notes

  • 1 Shi T-H, Wang M-X. CCS Chem. 2020; 2: 916
  • 2 Cheung KY, Segawa Y, Itami K. Chemistry 2020; DOI: 10.1002/chem.202002316.
  • 3 Eisenberg D, Shenhar R, Rabinovitz M. Chem. Soc. Rev. 2010; 39: 2879
  • 4 Gleiter R, Esser B, Kornmayer SC. Acc. Chem. Res. 2009; 42: 1108
  • 5 Esser B, Bandyopadhyay A, Rominger F, Gleiter R. Chemistry 2009; 15: 3368
  • 6 Tahara K, Tobe Y. Chem. Rev. 2006; 106: 5274
  • 7 Heilbronner E. Helv. Chim. Acta 1954; 37: 921
  • 8 Vögtle F. Top. Curr. Chem. 1983; 115: 157
  • 9 Kivelson S, Chapman OL. Phys. Rev. B: Condens. Matter 1983; 28: 7236
  • 10 Choi HS, Kim KS. Angew. Chem. Int. Ed. 1999; 38: 2256
  • 11 Wu CS, Lee PY, Chai JD. Sci. Rep. 2016; 6: 37249
  • 12 Sadowsky D, McNeill K, Cramer CJ. Faraday Discuss. 2010; 145: 507
  • 13 Chen Z, Jiang D-E, Lu X, Bettinger HF, Dai S, Schleyer Pv, Houk KN. Org. Lett. 2007; 9: 5449
  • 14 Battaglia S, Faginas-Lago N, Andrae D, Evangelisti S, Leininger T. J. Phys. Chem. A 2017; 121: 3746
  • 15 San-Fabián E, Pérez-Guardiola A, Moral M, Pérez-Jimenez AJ, Sancho-Garcίa JC. Advanced Magnetic and Optical Materials. Tiwari A, Iyer PK, Kumar V, Swart H. , Eds. Scrivener Publishing LLC; Beverly: 2017
  • 16 Omachi H, Nakayama T, Takahashi E, Segawa Y, Itami K. Nat. Chem. 2013; 5: 572
  • 17 Segawa Y, Yagi A, Ito H, Itami K. Org. Lett. 2016; 18: 1430
  • 18 Kohnke FH, Slawin AM. Z, Stoddart JF, Williams DJ. Angew. Chem. Int. Ed. 1987; 26: 892
  • 19 Ashton PR, Isaacs NS, Kohnke FH, Slawin AM. Z, Spencer CM, Stoddart JF, Williams DJ. Angew. Chem. Int. Ed. 1988; 27: 966
  • 20 Ashton PR, Brown GR, Isaacs NS, Giuffrida D, Kohnke FH, Mathias JP, Slawin AM. Z, Smith DR, Stoddart JF, Williams DJ. J. Am. Chem. Soc. 1992; 114: 6330
  • 21 Godt A, Enkelmann V, Schlüter A-D. Angew. Chem. Int. Ed. 1989; 28: 1680
  • 22 Cory RM, McPhail CL, Dikmans AJ, Vittal JJ. Tetrahedron Lett. 1996; 37: 1983
  • 23 Schulz F, Garcia F, Kaiser K, Pérez D, Guitián E, Gross L, Peña D. Angew. Chem. Int. Ed. 2019; 58: 9038
  • 24 Chen H, Gui S, Zhang Y, Liu Z, Miao Q. CCS Chem. 2020; 2: 613
  • 25 Shi T-H, Guo Q-H, Tong S, Wang M-X. J. Am. Chem. Soc. 2020; 142: 4576
  • 26 Shi T-H, Tong S, Wang M-X. Angew. Chem. Int. Ed. 2020; 59: 7700
  • 27 Zhang Y, Tong S. Angew. Chem. Int. Ed. 2020; DOI: 10.1002/anie.202006231.
  • 28 Zhang Q, Zhang Y-E, Tong S, Wang M-X. J. Am. Chem. Soc. 2020; 142: 1196
  • 29 Frisch MJ. , et al. Gaussian 09, Rev. D.01. Gaussian, Inc.; Wallingford: 2010
  • 30 Becke AD. Phys. Rev. A 1988; 38: 3098
  • 31 Becke AD. J. Chem. Phys. 1993; 98: 5648
  • 32 Yang W, Parr RG. Phys. Rev. B: Condens. Matter 1988; 37: 785
  • 33 Ditchfield R, Hehre WJ, Pople JA. J. Chem. Phys. 1971; 54: 72
  • 34 Hariharan PC, Pople JA. Theor. Chim. Acta 1973; 28: 213
  • 35 George P, Trachtman M, Bock CW, Brett AM. Tetrahedron 1976; 32: 317
  • 36 Minkin VI. Pure Appl. Chem. 1999; 71: 1919
  • 37 Different strain energies of belt[n]arenes were reported by the authors in the text and in the Supporting Information of the paper (cf. Ref. 17). We checked the data and found that reported in the Supporting Information is correct