Guest Encapsulation Scope of a Triptycene-Based Pd2L4 Coordination Cage

Shota Hasegawa; Ananya Baksi; Bin Chen; Guido H. Clever

doi:10.1055/a-1953-0155

Organic Materials, Inhaltsverzeichnis

CC BY-NC-ND 4.0 · Organic Materials 2022; 4(04): 222-227
DOI: 10.1055/a-1953-0155

Supramolecular Chemistry

Short Communication

Guest Encapsulation Scope of a Triptycene-Based Pd₂L₄ Coordination Cage

Authors

Shota Hasegawa

^aDepartment of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn Str. 6, 44227 Dortmund, Germany
Ananya Baksi

^aDepartment of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn Str. 6, 44227 Dortmund, Germany
Bin Chen

^aDepartment of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn Str. 6, 44227 Dortmund, Germany

^bState Key Laboratory of Radiation Medicine and Protection, Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou, P. R. of China
Guido H. Clever

^aDepartment of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn Str. 6, 44227 Dortmund, Germany

Abstract

Alle Artikel dieser Rubrik

Abstract

The scope of a lantern-shaped, triptycene-based Pd₂L₄ coordination cage to encapsulate various carbon-rich guests was investigated. The cage was found to bind two molecules of corannulene and a variety of C₆₀ derivatives in moderate to quantitative yields. Non-disruptive extraction of encapsulated fullerene derivative PC₆₁BM from the cage was demonstrated by the simple addition of CS₂ into an acetonitrile solution of the host–guest complex. This process can be accomplished in a layer-to-layer fashion, and thus, the recovered cage can be further utilized in a recycling process. As this self-assembled host is readily synthesized and able to transfer fullerenes and a range of its derivatives into polar organic solvents, it allows facilitating purification, chemical modification and solid-state processing of fullerenes for a range of materials applications.

Key words

supramolecular chemistry - host–guest complexes - fullerenes

Volltext

Referenzen

References and Notes
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25 To the NMR tube where an acetonitrile solution of Pd₂ 1 ₄ (0.70 mM, 0.600 mL, 0.42 µmol) was placed, excess solid corannulene was added and heated at 70 °C for 24 h. ¹H NMR (500 MHz, CD₃CN, 298 K): δ (ppm) e 8.35 (s, 16 H), d 8.03 (d, J = 8.8 Hz, 8H), f 7.86 (m, 8 H), b 7.82 (m, 8 H), c 7.48 (dd, J = 8.8, 5.7 Hz, 8 H), g 7.36 (dd, J = 5.3, 3.3 Hz, 8 H), h 6.61 (s, 8 H), a 6.00 (s, 8H), encapsulated corannulenes 5.47 (s, 20 H). ¹³C NMR (125 MHz, CD₃CN, 298 K): δ (ppm) 166.12, 165.70, 154.15, 152.99, 151.33, 150.30, 148.64, 147.74, 142.88, 142.40, 139.94, 138.09, 133.29, 132.40, 131.49, 130.95, 130.35, 130.16, 128.66, 127.49, 126.89, 126.27, 125.91, 121.68, 120.64, 54.94, 54.54 (12 signals out of 13 signals from empty Pd₂ 1 ₄). DOSY: Diffusion coefficient D of corannulenes inside Pd₂ 1 ₄ and free corannulene in the same solution were estimated to be 6.69 × 10⁻¹⁰ and 18.58 × 10⁻¹⁰ m² · s⁻¹, respectively. ESI MS (positive): found: 724.6237; calculated for [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₂₀H₁₀)₂]⁴⁺ to be 724.6248
26 Schmidt BM, Osuga T, Sawada T, Hoshino M, Fujita M. Angew. Chem. Int. Ed. 2015; 55: 1561

27 General procedure: To an acetonitrile solution of Pd₂ 1 ₄ (0.35 mM, 1.0 mL, 0.35 µmol) in a vial was added an excess amount of solid guest. The heterogeneous mixture was stirred under heating at 70 °C for 24 h. After the reaction, the residual solid guest was removed by filtration. The yields were estimated from the ¹H NMR integral ratio.
2@Pd₂ 1 ₄: ¹H NMR (500 MHz, CD₃CN, 298 K): δ (ppm) b 8.38 (d, J = 5.2 Hz, 4 H), b 8.37 (d, J = 5.2 Hz, 4 H), d 8.32 (ddd, J = 8.5, 2.2, 1.2 Hz, 4 H), d 8.27 (ddd, J = 8.5, 2.2, 1.2 Hz, 4 H), e*2 8.22 (s, 8 H), e 7.97 (s, 4 H), e 7.87 (s, 4 H), c 7.78 (dd, J = 8.5, 5.6 Hz, 4 H), c 7.74 (dd, J = 8.5, 5.6 Hz, 4 H), f*4 7.73 – 7.64 (m, 8 H), a 7.34 (d, J = 2.1 Hz, 4 H), g*4 7.26 – 7.20 (m, 8 H), a 7.10 (d, J = 2.1 Hz, 4 H), h 6.43 (s, 2 H), h 6.37 (s, 2 H), h 6.27 (s, 2 H), h 6.20 (s, 2 H), i 4.06 (s, 4 H), j 3.57 (s, 3 H). ¹³C NMR (150 MHz, CD₃CN, 298 K): δ (ppm) 166.15, 166.00, 165.71, 165.60, 154.38, 153.71, 153.49, 153.44, 153.30, 152.23, 152.15, 147.56, 147.45, 146.51, 146.10, 145.73, 145.18, 144.80, 144.15, 144.02, 143.35, 143.01, 142.99, 142.83, 142.81, 142.27, 142.13, 142.03, 141.02, 140.74, 140.28, 140.16, 138.79, 135.51, 132.62, 132.13, 131.09, 131.06, 130.96, 130.61, 129.45, 129.04, 127.76, 127.74, 127.70, 127.69, 126.24, 126.20, 126.16, 126.01, 121.91, 121.76, 121.58, 121.55, 71.41, 69.57, 54.77, 54.70, 54.58, 42.11. DOSY: Diffusion coefficient D = 5.26 × 10⁻¹⁰ m² · s⁻¹, and hydrodynamic radius r _H was calculated to be 12.4 Å. ESI MS (positive): found: 794.0999 and 1087.7986; calculated for [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₆₃NH₇)]⁴⁺ and [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₆₃NH₇)(BF₄)]³⁺ to be 794.1005 and 1087.8021, respectively.
3@Pd₂ 1 ₄: ¹H NMR (500 MHz, CD₃CN, 298 K): δ (ppm) b 8.63 (d, J = 5.2 Hz, 4 H), b 8.36 (d, J = 5.2 Hz, 4 H), e 8.32 (s, 4 H), d 8.28 (ddd, J = 8.5, 2.2, 1.2 Hz, 4 H), d 8.26 (ddd, J = 8.5, 2.2, 1.2 Hz, 4 H), e 8.12 (s, 4 H), e 8.07 (s, 4 H), k/l 7.99 (m, 2 H), k/l 7.94 (m, 2 H), c 7.80 (dd, J = 8.5, 5.6 Hz, 4 H), e 7.79 (s, 4 H), c 7.70 (dd, J = 8.5, 5.6 Hz, 4 H), f*4 7.70 – 7.61 (m, 8 H), a 7.54 (d, J = 2.1 Hz, 4 H), a 7.50 (d, J = 2.1 Hz, 4 H), g*4 7.26 – 7.17 (m, 8 H), h 6.50 (s, 2 H), h 6.37 (s, 2 H), h 6.20 (s, 2 H), h 6.15 (s, 2 H), i 4.44 (s, 2 H), j 3.04 (m, 1 H), j 2.71 (m, 1 H). ¹³C NMR (150 MHz, CD₃CN, 298 K): δ (ppm) 166.16, 166.13, 165.96, 165.68, 165.51, 156.20, 155.44, 153.78, 153.51, 153.36, 153.09, 153.01, 152.48, 151.80, 150.25, 148.66, 148.26, 147.15, 146.57, 146.51, 146.10, 145.71, 145.64, 145.52, 145.26, 145.01, 144.96, 144.76, 144.71, 144.19, 143.85, 143.84, 143.16, 143.11, 143.04, 143.02, 142.97, 142.85, 142.83, 142.61, 142.40, 142.34, 142.13, 142.03, 141.97, 141.13, 140.99, 140.72, 140.48, 140.47, 139.29, 138.21, 138.04, 137.23, 136.41, 132.94, 132.63, 132.48, 131.07, 131.03, 130.90, 130.68, 130.37, 129.42, 129.26, 129.23, 128.37, 127.70, 127.66, 127.53, 126.24, 126.22, 126.02, 125.96, 125.19, 121.83, 121.63, 121.59, 121.30, 120.71, 76.22, 58.71, 54.85, 54.79, 54.64, 54.48 (13 signals from empty Pd₂ 1 ₄). DOSY: Diffusion coefficient D = 5.47 × 10⁻¹⁰ m² · s⁻¹, and hydrodynamic radius r _H was calculated to be 12.0 Å. ESI MS (positive): found: 808.8505 and 1107.4664; calculated for [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₆₉H₈)]⁴⁺ and [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₆₉H₈)(BF₄)]³⁺ to be 808.8518 and 1107.4704, respectively.
4@Pd₂ 1 ₄: ¹H NMR (500 MHz, CD₃CN, 298 K): δ (ppm) b 8.60 (d, J = 5.2 Hz, 4 H), b 8.38 (d, J = 5.2 Hz, 4 H), d 8.33 (ddd, J = 8.5, 2.2, 1.2 Hz, 4 H), d 8.31 (ddd, J = 8.5, 2.2, 1.2 Hz, 4 H), e 8.24 (s, 4 H), n 8.12 (m, 2 H), e*2 8.09 (s, 8 H), e 7.90 (s, 4 H), o 7.89 (m, 1 H) c 7.81 (dd, J = 8.5, 5.6 Hz, 4 H), c 7.76 (dd, J = 8.5, 5.6 Hz, 4 H), f*4&m 7.74 – 7.61(m, 10 H), a 7.56 (d, J = 2.1 Hz, 4 H), a 7.54 (d, J = 2.1 Hz, 4 H), g*4 7.26 – 7.18 (m, 8 H), h 6.45(s, 2 H), h 6.33 (s, 2 H), h 6.32 (s, 2 H), h 6.19 (s, 2 H), i 3.68 (s, 3 H), j 2.52 (m, 2 H), l 2.31 (m, 2 H), k 2.00 (m, 2 H). ¹³C NMR (176 MHz, CD₃CN, 298 K): δ (ppm) 174.35, 166.17, 166.01, 165.96, 165.68, 165.57, 153.66, 153.65, 153.52, 153.45, 153.11, 152.61, 151.93, 150.26, 149.26, 148.70, 148.12, 147.44, 145.07, 144.91, 144.79, 144.33, 144.12, 144.09, 144.07, 143.96, 143.86, 143.48, 143.24, 143.18, 143.09, 142.99, 142.93, 142.82, 142.80, 142.72, 142.68, 142.62, 142.52, 142.21, 142.05, 141.86, 141.71, 141.59, 140.86, 140.72, 140.70, 140.54, 140.47, 140.41, 139.70, 138.05, 136.80, 136.62, 135.72, 132.88, 132.71, 132.63, 132.51, 131.11, 131.07, 131.03, 130.73, 130.39, 130.33, 130.11, 129.61, 129.24, 128.39, 127.76, 127.73, 127.55, 126.35, 126.25, 126.20, 125.98, 121.73, 121.59, 120.77, 120.72, 81.63, 54.81, 54.72, 54.66, 54.52, 54.50, 54.35, 52.21, 34.41, 33.80, 23.42 (13 signals from empty Pd₂ 1 ₄). DOSY: Diffusion coefficient D = 5.38 × 10⁻¹⁰ m² · s⁻¹, and hydrodynamic radius r _H was calculated to be 12.1 Å. ESI MS (positive): found: 827.3594 and 1132.1460; calculated for [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₇₂H₁₄O₂)]⁴⁺ and [(C₃₄H₁₈ N₄O₄)₄Pd₂(C₇₂H₁₄O₂)(BF₄)]³⁺ to be 827.3610 and 1132.1494, respectively.

28 Yoshizawa M, Klosterman JK, Fujita M. Angew. Chem. Int. Ed. 2009; 48: 3418

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