A Novel [60]Fullerene-Calixarene Conjugate Which Facilitates Self-Inclusion of the [60]Fullerene Moiety into the Homooxacalix[3]arene Cavity

Photoinduced Electron Transfer between C60-Pendant Calixarene and Captured Electron Donor: Improvement of Electron-Transfer Efficiency by Applying Host−Guest Chemistry

“…Parts a and b of Figure show the 1 H NMR spectra of ammonium aniline and calix-C 60 in CDCl 3 , respectively. Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II ; Scheme a) . With the addition of ammonium aniline, the 1 H NMR signals of calix-C 60 and ammonium aniline changed significantly; the 1 H NMR signals of conformer I decreased and the NMR signals of conformer II and ammonium aniline varied as shown in parts c and d of Figures .…”

“…The aniline-moiety is arranged in the direction of the upper rim of calixarene moiety. 1 H NMR peaks were assigned from observations of 1 H− 1 H 2D COSY and 1 H VT NMR. , These 1 H NMR measurements in the presence of sufficient ammonium aniline have shown that calix-C 60 can make a linked dyad molecule with ammonium aniline and exists predominantly as conformer II with its calixarene cavity occupied by the ammonium moiety of ammonium aniline.

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1

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“…Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II; Scheme 2a). 6 With the addition of ammonium aniline, the reported that homooxacalixarenes can include an ammonium group of n-BuNH 3 + from the direction of its phenyl groups (upper rim). 5 From the changes of 1 H NMR signals, it can be deduced that the binding species between conformer II and ammonium aniline exists as shown in Scheme 2b.…”

“…Homooxa[3]calixarene-C 60 -connected molecule (calix-C 60 ; Scheme 1a) and a reference C 60 derivative (ref-C 60 ; Scheme 1c) were prepared by the method described in our previous paper. 6 The primary ammonium derivative of Nmethylaniline (ammonium-aniline; Scheme 1b) was obtained by the protonation of the corresponding N-(3-aminopropyl)-Nmethylaniline (Tokyo Kasei Kogyo Co. Ltd.) with one equimolar of HCl. The product was recrystallized twice by methanol and ether and dried under vacuo at room temperature in the dark.…”

Photoinduced Electron Transfer between C60-Pendant Calixarene and Captured Electron Donor: Improvement of Electron-Transfer Efficiency by Applying Host−Guest Chemistry

“…Parts a and b of Figure show the 1 H NMR spectra of ammonium aniline and calix-C 60 in CDCl 3 , respectively. Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II ; Scheme a) . With the addition of ammonium aniline, the 1 H NMR signals of calix-C 60 and ammonium aniline changed significantly; the 1 H NMR signals of conformer I decreased and the NMR signals of conformer II and ammonium aniline varied as shown in parts c and d of Figures .…”

“…The aniline-moiety is arranged in the direction of the upper rim of calixarene moiety. 1 H NMR peaks were assigned from observations of 1 H− 1 H 2D COSY and 1 H VT NMR. , These 1 H NMR measurements in the presence of sufficient ammonium aniline have shown that calix-C 60 can make a linked dyad molecule with ammonium aniline and exists predominantly as conformer II with its calixarene cavity occupied by the ammonium moiety of ammonium aniline.

2

1

…”

“…Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II; Scheme 2a). 6 With the addition of ammonium aniline, the reported that homooxacalixarenes can include an ammonium group of n-BuNH 3 + from the direction of its phenyl groups (upper rim). 5 From the changes of 1 H NMR signals, it can be deduced that the binding species between conformer II and ammonium aniline exists as shown in Scheme 2b.…”

“…Homooxa[3]calixarene-C 60 -connected molecule (calix-C 60 ; Scheme 1a) and a reference C 60 derivative (ref-C 60 ; Scheme 1c) were prepared by the method described in our previous paper. 6 The primary ammonium derivative of Nmethylaniline (ammonium-aniline; Scheme 1b) was obtained by the protonation of the corresponding N-(3-aminopropyl)-Nmethylaniline (Tokyo Kasei Kogyo Co. Ltd.) with one equimolar of HCl. The product was recrystallized twice by methanol and ether and dried under vacuo at room temperature in the dark.…”

Nucleophilic cyclopropanation of [60]fullerene by the addition–elimination mechanism

“…The separately prepared hydroxy-containing fullerene block 238 was fused by the carbodiimide method with the homooxacalix [3]arene moiety to give compound 239, which exhibits interesting selfcomplexation-decomplexation properties in response to the solvent polarity (Scheme 67). 126 A macrocycle having two isosteviol moieties and malonate fragment was synthesized and its ability to inhibit the growth of Mycobacterium tuberculosis H37Rv in vitro at a minimum concentration of 1 mg  cm À3 was demonstrated. The macrocycle and the acyclic analogue add fullerene C 60 at the activated methylene group to furnish the corresponding methanofullerene conjugates 240 and 241 (Scheme 68).…”

Photoinduced Electron Transfer between C60-Pendant Calixarene and Captured Electron Donor: Improvement of Electron-Transfer Efficiency by Applying Host−Guest Chemistry

“…Parts a and b of Figure show the 1 H NMR spectra of ammonium aniline and calix-C 60 in CDCl 3 , respectively. Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II ; Scheme a) . With the addition of ammonium aniline, the 1 H NMR signals of calix-C 60 and ammonium aniline changed significantly; the 1 H NMR signals of conformer I decreased and the NMR signals of conformer II and ammonium aniline varied as shown in parts c and d of Figures .…”

“…The aniline-moiety is arranged in the direction of the upper rim of calixarene moiety. 1 H NMR peaks were assigned from observations of 1 H− 1 H 2D COSY and 1 H VT NMR. , These 1 H NMR measurements in the presence of sufficient ammonium aniline have shown that calix-C 60 can make a linked dyad molecule with ammonium aniline and exists predominantly as conformer II with its calixarene cavity occupied by the ammonium moiety of ammonium aniline.

2

1

…”

“…Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II; Scheme 2a). 6 With the addition of ammonium aniline, the reported that homooxacalixarenes can include an ammonium group of n-BuNH 3 + from the direction of its phenyl groups (upper rim). 5 From the changes of 1 H NMR signals, it can be deduced that the binding species between conformer II and ammonium aniline exists as shown in Scheme 2b.…”

“…Homooxa[3]calixarene-C 60 -connected molecule (calix-C 60 ; Scheme 1a) and a reference C 60 derivative (ref-C 60 ; Scheme 1c) were prepared by the method described in our previous paper. 6 The primary ammonium derivative of Nmethylaniline (ammonium-aniline; Scheme 1b) was obtained by the protonation of the corresponding N-(3-aminopropyl)-Nmethylaniline (Tokyo Kasei Kogyo Co. Ltd.) with one equimolar of HCl. The product was recrystallized twice by methanol and ether and dried under vacuo at room temperature in the dark.…”

Nucleophilic cyclopropanation of [60]fullerene by the addition–elimination mechanism

“…The separately prepared hydroxy-containing fullerene block 238 was fused by the carbodiimide method with the homooxacalix [3]arene moiety to give compound 239, which exhibits interesting selfcomplexation-decomplexation properties in response to the solvent polarity (Scheme 67). 126 A macrocycle having two isosteviol moieties and malonate fragment was synthesized and its ability to inhibit the growth of Mycobacterium tuberculosis H37Rv in vitro at a minimum concentration of 1 mg  cm À3 was demonstrated. The macrocycle and the acyclic analogue add fullerene C 60 at the activated methylene group to furnish the corresponding methanofullerene conjugates 240 and 241 (Scheme 68).…”

Photoinduced Electron Transfer between C60-Pendant Calixarene and Captured Electron Donor: Improvement of Electron-Transfer Efficiency by Applying Host−Guest Chemistry

“…Parts a and b of Figure show the 1 H NMR spectra of ammonium aniline and calix-C 60 in CDCl 3 , respectively. Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II ; Scheme a) . With the addition of ammonium aniline, the 1 H NMR signals of calix-C 60 and ammonium aniline changed significantly; the 1 H NMR signals of conformer I decreased and the NMR signals of conformer II and ammonium aniline varied as shown in parts c and d of Figures .…”

“…The aniline-moiety is arranged in the direction of the upper rim of calixarene moiety. 1 H NMR peaks were assigned from observations of 1 H− 1 H 2D COSY and 1 H VT NMR. , These 1 H NMR measurements in the presence of sufficient ammonium aniline have shown that calix-C 60 can make a linked dyad molecule with ammonium aniline and exists predominantly as conformer II with its calixarene cavity occupied by the ammonium moiety of ammonium aniline.

2

1

…”

“…Calix-C 60 gives a complicated 1 H NMR spectrum reflecting the mixture of two environmentally sensitive types of conformers (formation of self-inclusion complex) in CDCl 3 (conformers I and II; Scheme 2a). 6 With the addition of ammonium aniline, the reported that homooxacalixarenes can include an ammonium group of n-BuNH 3 + from the direction of its phenyl groups (upper rim). 5 From the changes of 1 H NMR signals, it can be deduced that the binding species between conformer II and ammonium aniline exists as shown in Scheme 2b.…”

“…Homooxa[3]calixarene-C 60 -connected molecule (calix-C 60 ; Scheme 1a) and a reference C 60 derivative (ref-C 60 ; Scheme 1c) were prepared by the method described in our previous paper. 6 The primary ammonium derivative of Nmethylaniline (ammonium-aniline; Scheme 1b) was obtained by the protonation of the corresponding N-(3-aminopropyl)-Nmethylaniline (Tokyo Kasei Kogyo Co. Ltd.) with one equimolar of HCl. The product was recrystallized twice by methanol and ether and dried under vacuo at room temperature in the dark.…”

Nucleophilic cyclopropanation of [60]fullerene by the addition–elimination mechanism

“…The separately prepared hydroxy-containing fullerene block 238 was fused by the carbodiimide method with the homooxacalix [3]arene moiety to give compound 239, which exhibits interesting selfcomplexation-decomplexation properties in response to the solvent polarity (Scheme 67). 126 A macrocycle having two isosteviol moieties and malonate fragment was synthesized and its ability to inhibit the growth of Mycobacterium tuberculosis H37Rv in vitro at a minimum concentration of 1 mg  cm À3 was demonstrated. The macrocycle and the acyclic analogue add fullerene C 60 at the activated methylene group to furnish the corresponding methanofullerene conjugates 240 and 241 (Scheme 68).…”