Flexible decapyrrylcorannulene hosts

Affiliations

¹ State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
² State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. xmuzhangqy@xmu.edu.cn.
³ Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, 230026, China. sfyang@ustc.edu.cn.
⁴ State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. syxie@xmu.edu.cn.

PMID: 30700716
PMCID: PMC6353959
DOI: 10.1038/s41467-019-08343-6

Flexible decapyrrylcorannulene hosts

Yun-Yan Xu et al. Nat Commun. 2019.

. 2019 Jan 30;10(1):485.

doi: 10.1038/s41467-019-08343-6.

Authors

Affiliations

¹ State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
² State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. xmuzhangqy@xmu.edu.cn.
³ Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, 230026, China. sfyang@ustc.edu.cn.
⁴ State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. syxie@xmu.edu.cn.

PMID: 30700716
PMCID: PMC6353959
DOI: 10.1038/s41467-019-08343-6

Abstract

The assembly of spherical fullerenes, or buckyballs, into single crystals for crystallographic identification often suffers from disordered arrangement. Here we show a chiral configuration of decapyrrylcorannulene that has a concave 'palm' of corannulene and ten flexible electron-rich pyrryl group 'fingers' to mimic the smart molecular 'hands' for self-adaptably cradling various buckyballs in a (+)hand-ball-hand(-) mode. As exemplified by crystallographic identification of 15 buckyball structures representing pristine, exohedral, endohedral, dimeric and hetero-derivatization, the pyrryl groups twist with varying dihedral angles to adjust the interaction between decapyrrylcorannulene and fullerene. The self-adaptable electron-rich pyrryl groups, susceptible to methylation, are theoretically revealed to contribute more than the bowl-shaped palm of the corannulene in holding buckyball structures. The generality of the present decapyrrylcorannulene host with flexible pyrryl groups facilitates the visualization of numerous unknown/unsolved fullerenes by crystallography and the assembly of the otherwise close-packed spherical fullerenes into two-dimensional layered structures by intercalation.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing interests.

Figures

**Fig. 1**
Synthesis of decapyrrylcorannulene derivatives 2 from decachlorocorannulene 1. Conditions: NaH (60% oil dispersion, 2.0 mmol, 12 eq for 2a, 3.4 mmol, 20 eq for 2b), pyrrole (2.0 mmol, 12 eq) or 3,4-dimethylpyrrol (3.4 mmol, 20 eq), decachlorocorannulene 1 (0.17 mmol, 1 eq), 25 °C, 12 h. DMF: N,N-dimethylformamide

**Fig. 2**
Crystallographic structures and packing of 2a and 2b. a, c Crystallographic structures of 2a and 2b with thermal ellipsoids at the 50% probability level. The bowl depths of 2a and 2b are indicated. b, d Packing structures of 2a in the a–c plane and 2b in the b–c plane. C atom is shown in gold and N atom in navy blue. All hydrogen atoms are omitted for clarity

**Fig. 3**
Crystallographic structure and packing of 2DPC{C₆₀}. a Side view of 2DPC{C₆₀}. b Packing structure of 2DPC{C₆₀} in the *b–c* plane. C atom in 2a is shown in gold, C₆₀ in grey and N atom in navy blue. All hydrogen atoms and solvent molecules (CS₂) are omitted for clarity

**Fig. 4**
Crystallographic structures of co-crystals between DPC (2a) and fullerenes. a 2DPC{C₆₀}, b 2DPC{C₇₀}, c 2DPC{C₉₀}, d 2DPC{α-PC₇₁BM}, e 2DPC{β₁-PC₇₁BM}, f 2DPC{PC₆₁P}, g 2DPC{PC₆₁AE}, h 2DPC{C_s-C₇₁H₂-I}, i 2DPC{C_s-C₇₁H₂-II}, j 2DPC{C₆₅H₆}, k 2DPC{C₆₀HPh}, l 2DPC{C₆₀HCH₃}, m 2DPC{C_2v-C₇₁H₂-III}, n 2DPC{Sc₃N@C₈₀}, o 2DPC{(C₅₉N)₂}. PC₆₁P: [6,6]-phenyl-C₆₁-pyridyl. PC₆₁AE: [6,6]-pyridyl-C₆₁-acetic acid ethyl ester. C atom is shown in gold, N atom in navy blue, Sc atom in green, and O atom in red. All hydrogen atoms and solvent molecules in the crystal structures have been omitted for clarity

**Fig. 5**
Layered structure of the co-crystal formed between DPC (2a) and C₆₀. a, b Edge-on view (a) and top view (b) of the space-filling structure of C₆₀ and the stick structure of DPC. FL is a monolayer of C₆₀, and DL is a slightly corrugated double DPC layer. C atom is shown in gold, N atom in navy blue, and C₆₀ in purple. All hydrogens and solvent molecules (CS₂) in the co-crystal have been omitted for clarity

**Fig. 6**
The total interaction energies and partial interaction energies for six representative co-crystals. All values in the figure are absolute values. ∆E^int_F/2DPC (black columns), ∆E^int_F/P (red columns), and ∆E^int_F/C (blue columns) represent the interaction energies between fullerene (F) and both hosts (2DPC), fullerene (F) and pyrryl groups (P), and fullerene (F) and corannulene part (C), respectively

See this image and copyright information in PMC

References

1. Kroto HW, Heath JR, O’Brien SC, Curl RF, Smalley RE. C60: buckminsterfullerene. Nature. 1985;318:162–163. doi: 10.1038/318162a0. - DOI
1. Iiduka Y, et al. Structural determination of metallofullerene Sc3C82 revisited: a surprising finding. J. Am. Chem. Soc. 2005;127:12500–12501. doi: 10.1021/ja054209u. - DOI - PubMed
1. Lu X, et al. Structural elucidation and regioselective functionalization of an unexplored carbide cluster metallofullerene Sc2C2@CS(6)-C82. J. Am. Chem. Soc. 2011;133:19553–19558. doi: 10.1021/ja208841w. - DOI - PubMed
1. Yamada M, et al. Sc2@C66 revisited: an endohedral fullerene with scandium ions nestled within two unsaturated linear triquinanes. J. Am. Chem. Soc. 2014;136:7611–7614. doi: 10.1021/ja5035649. - DOI - PubMed
1. Hawkins JM, Meyer A, Lewis TA, Loren S, Hollander FJ. Crystal structure of osmylated C60: confirmation of the soccer ball framework. Science. 1991;252:312–313. doi: 10.1126/science.252.5003.312. - DOI - PubMed

Publication types

Actions

LinkOut - more resources

Full Text Sources
Research Materials
- NCI CPTC Antibody Characterization Program

Save citation to file

Email citation

Add to Collections

Add to My Bibliography

Your saved search

Create a file for external citation management software

Your RSS Feed

Flexible decapyrrylcorannulene hosts

Affiliations

Flexible decapyrrylcorannulene hosts

Authors

Affiliations

Abstract

Conflict of interest statement

Figures

References

Publication types

LinkOut - more resources

Full Text Sources

Research Materials