Synthesis, characterization, and small hydrocarbon encapsulation of dicavitand-porphyrins

Jun Nakazawa, Jun Hagiwara, Yuichi Shimazaki, Fumito Tani, Yoshinori Naruta

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

New host molecules "Dicavitand-Porphyrins" [H 2C 2P(syn,syn) (3), H 2C 2P(syn,anti) (4)] with small cavities on one or both sides of the porphyrin plane were synthesized from 5,10-bis(2,6-dihydroxyphenyl)-15,20-diphenylporphyrin and bis(chloromethyl) cavitand in 15 and 34% yield, respectively. Similarity of guest size selectivity of the host 4 in comparison with the reported "Cavitand-porphyrin" [H 2CP(syn) (1)] suggests that these hosts have the same cavity size. The 1:1 and 1:2 association constants (K 11 and K 12) of the guest encapsulations into 3 were also obtained by 1HNMR titration and nonlinear least square fittings. The guest size dependences of K 11 and K 12 values of 3 show that the initial cavity prefers larger guests such as ethane, while the second one does not. The induced-fit type very small structural changes (estimated within 1°) upon first guest encapsulation of the host 3 affects the guest encapsulation of the other cavity through the covalent linkages.

Original languageEnglish
Pages (from-to)912-919
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume85
Issue number8
DOIs
Publication statusPublished - Aug 27 2012

Fingerprint

Porphyrins
Hydrocarbons
Encapsulation
Ethane
Titration
Association reactions
Molecules
cavitand

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Synthesis, characterization, and small hydrocarbon encapsulation of dicavitand-porphyrins. / Nakazawa, Jun; Hagiwara, Jun; Shimazaki, Yuichi; Tani, Fumito; Naruta, Yoshinori.

In: Bulletin of the Chemical Society of Japan, Vol. 85, No. 8, 27.08.2012, p. 912-919.

Research output: Contribution to journalArticle

Nakazawa, Jun ; Hagiwara, Jun ; Shimazaki, Yuichi ; Tani, Fumito ; Naruta, Yoshinori. / Synthesis, characterization, and small hydrocarbon encapsulation of dicavitand-porphyrins. In: Bulletin of the Chemical Society of Japan. 2012 ; Vol. 85, No. 8. pp. 912-919.
@article{a8e9c8ee2df0456e8cbc4cd20dc72a09,
title = "Synthesis, characterization, and small hydrocarbon encapsulation of dicavitand-porphyrins",
abstract = "New host molecules {"}Dicavitand-Porphyrins{"} [H 2C 2P(syn,syn) (3), H 2C 2P(syn,anti) (4)] with small cavities on one or both sides of the porphyrin plane were synthesized from 5,10-bis(2,6-dihydroxyphenyl)-15,20-diphenylporphyrin and bis(chloromethyl) cavitand in 15 and 34{\%} yield, respectively. Similarity of guest size selectivity of the host 4 in comparison with the reported {"}Cavitand-porphyrin{"} [H 2CP(syn) (1)] suggests that these hosts have the same cavity size. The 1:1 and 1:2 association constants (K 11 and K 12) of the guest encapsulations into 3 were also obtained by 1HNMR titration and nonlinear least square fittings. The guest size dependences of K 11 and K 12 values of 3 show that the initial cavity prefers larger guests such as ethane, while the second one does not. The induced-fit type very small structural changes (estimated within 1°) upon first guest encapsulation of the host 3 affects the guest encapsulation of the other cavity through the covalent linkages.",
author = "Jun Nakazawa and Jun Hagiwara and Yuichi Shimazaki and Fumito Tani and Yoshinori Naruta",
year = "2012",
month = "8",
day = "27",
doi = "10.1246/bcsj.20120107",
language = "English",
volume = "85",
pages = "912--919",
journal = "Bulletin of the Chemical Society of Japan",
issn = "0009-2673",
publisher = "The Chemical Society of Japan",
number = "8",

}

TY - JOUR

T1 - Synthesis, characterization, and small hydrocarbon encapsulation of dicavitand-porphyrins

AU - Nakazawa, Jun

AU - Hagiwara, Jun

AU - Shimazaki, Yuichi

AU - Tani, Fumito

AU - Naruta, Yoshinori

PY - 2012/8/27

Y1 - 2012/8/27

N2 - New host molecules "Dicavitand-Porphyrins" [H 2C 2P(syn,syn) (3), H 2C 2P(syn,anti) (4)] with small cavities on one or both sides of the porphyrin plane were synthesized from 5,10-bis(2,6-dihydroxyphenyl)-15,20-diphenylporphyrin and bis(chloromethyl) cavitand in 15 and 34% yield, respectively. Similarity of guest size selectivity of the host 4 in comparison with the reported "Cavitand-porphyrin" [H 2CP(syn) (1)] suggests that these hosts have the same cavity size. The 1:1 and 1:2 association constants (K 11 and K 12) of the guest encapsulations into 3 were also obtained by 1HNMR titration and nonlinear least square fittings. The guest size dependences of K 11 and K 12 values of 3 show that the initial cavity prefers larger guests such as ethane, while the second one does not. The induced-fit type very small structural changes (estimated within 1°) upon first guest encapsulation of the host 3 affects the guest encapsulation of the other cavity through the covalent linkages.

AB - New host molecules "Dicavitand-Porphyrins" [H 2C 2P(syn,syn) (3), H 2C 2P(syn,anti) (4)] with small cavities on one or both sides of the porphyrin plane were synthesized from 5,10-bis(2,6-dihydroxyphenyl)-15,20-diphenylporphyrin and bis(chloromethyl) cavitand in 15 and 34% yield, respectively. Similarity of guest size selectivity of the host 4 in comparison with the reported "Cavitand-porphyrin" [H 2CP(syn) (1)] suggests that these hosts have the same cavity size. The 1:1 and 1:2 association constants (K 11 and K 12) of the guest encapsulations into 3 were also obtained by 1HNMR titration and nonlinear least square fittings. The guest size dependences of K 11 and K 12 values of 3 show that the initial cavity prefers larger guests such as ethane, while the second one does not. The induced-fit type very small structural changes (estimated within 1°) upon first guest encapsulation of the host 3 affects the guest encapsulation of the other cavity through the covalent linkages.

UR - http://www.scopus.com/inward/record.url?scp=84865208391&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84865208391&partnerID=8YFLogxK

U2 - 10.1246/bcsj.20120107

DO - 10.1246/bcsj.20120107

M3 - Article

AN - SCOPUS:84865208391

VL - 85

SP - 912

EP - 919

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 8

ER -