Preorientation of olefins toward a single photodimer: Cucurbituril-mediated photodimerization of protonated azastilbenes in water

Murthy V S N Maddipatla, Lakshmi S. Kaanumalle, Arunkumar Natarajan, Mahesh Pattabiraman, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticle

86 Citations (Scopus)

Abstract

With the view to establishing the generality of cucurbit[8]uril as a template, the photodimerization of hydrochloride salts of eight azastilbenes has been investigated in an aqueous medium. Whereas in solution upon excitation all of these olefins yield products of geometric isomerization, cyclization, and hydration, in the presence of cucurbit[8]uril the predominant product is that of dimerization. Such a change in product distribution is attributed to the localization of the olefins by the host cucurbit[8]uril. Most importantly, instead of a mixture of dimers, predominantly a single dimer was obtained in each case. The nature of the dimer that was formed could be rationalized on the basis of the principles of "best fit" and "minimization of electrostatic repulsion". The superior ability of cucurbit[8]uril compared to micelles to act as a templating agent is attributed to its ability to provide a reaction cavity that is tight and time-independent.

Original languageEnglish
Pages (from-to)7545-7554
Number of pages10
JournalLangmuir
Volume23
Issue number14
DOIs
StatePublished - Jul 3 2007

Fingerprint

Alkenes
Dimers
alkenes
Olefins
dimers
Water
products
water
Dimerization
Cyclization
hydrochlorides
dimerization
Isomerization
Hydration
Micelles
isomerization
hydration
Electrostatics
micelles
templates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Preorientation of olefins toward a single photodimer : Cucurbituril-mediated photodimerization of protonated azastilbenes in water. / Maddipatla, Murthy V S N; Kaanumalle, Lakshmi S.; Natarajan, Arunkumar; Pattabiraman, Mahesh; Ramamurthy, Vaidhyanathan.

In: Langmuir, Vol. 23, No. 14, 03.07.2007, p. 7545-7554.

Research output: Contribution to journalArticle

Maddipatla, Murthy V S N ; Kaanumalle, Lakshmi S. ; Natarajan, Arunkumar ; Pattabiraman, Mahesh ; Ramamurthy, Vaidhyanathan. / Preorientation of olefins toward a single photodimer : Cucurbituril-mediated photodimerization of protonated azastilbenes in water. In: Langmuir. 2007 ; Vol. 23, No. 14. pp. 7545-7554.
@article{da5951707f3e427ebb19519872ad6d08,
title = "Preorientation of olefins toward a single photodimer: Cucurbituril-mediated photodimerization of protonated azastilbenes in water",
abstract = "With the view to establishing the generality of cucurbit[8]uril as a template, the photodimerization of hydrochloride salts of eight azastilbenes has been investigated in an aqueous medium. Whereas in solution upon excitation all of these olefins yield products of geometric isomerization, cyclization, and hydration, in the presence of cucurbit[8]uril the predominant product is that of dimerization. Such a change in product distribution is attributed to the localization of the olefins by the host cucurbit[8]uril. Most importantly, instead of a mixture of dimers, predominantly a single dimer was obtained in each case. The nature of the dimer that was formed could be rationalized on the basis of the principles of {"}best fit{"} and {"}minimization of electrostatic repulsion{"}. The superior ability of cucurbit[8]uril compared to micelles to act as a templating agent is attributed to its ability to provide a reaction cavity that is tight and time-independent.",
author = "Maddipatla, {Murthy V S N} and Kaanumalle, {Lakshmi S.} and Arunkumar Natarajan and Mahesh Pattabiraman and Vaidhyanathan Ramamurthy",
year = "2007",
month = "7",
day = "3",
doi = "10.1021/la700803k",
language = "English",
volume = "23",
pages = "7545--7554",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Preorientation of olefins toward a single photodimer

T2 - Cucurbituril-mediated photodimerization of protonated azastilbenes in water

AU - Maddipatla, Murthy V S N

AU - Kaanumalle, Lakshmi S.

AU - Natarajan, Arunkumar

AU - Pattabiraman, Mahesh

AU - Ramamurthy, Vaidhyanathan

PY - 2007/7/3

Y1 - 2007/7/3

N2 - With the view to establishing the generality of cucurbit[8]uril as a template, the photodimerization of hydrochloride salts of eight azastilbenes has been investigated in an aqueous medium. Whereas in solution upon excitation all of these olefins yield products of geometric isomerization, cyclization, and hydration, in the presence of cucurbit[8]uril the predominant product is that of dimerization. Such a change in product distribution is attributed to the localization of the olefins by the host cucurbit[8]uril. Most importantly, instead of a mixture of dimers, predominantly a single dimer was obtained in each case. The nature of the dimer that was formed could be rationalized on the basis of the principles of "best fit" and "minimization of electrostatic repulsion". The superior ability of cucurbit[8]uril compared to micelles to act as a templating agent is attributed to its ability to provide a reaction cavity that is tight and time-independent.

AB - With the view to establishing the generality of cucurbit[8]uril as a template, the photodimerization of hydrochloride salts of eight azastilbenes has been investigated in an aqueous medium. Whereas in solution upon excitation all of these olefins yield products of geometric isomerization, cyclization, and hydration, in the presence of cucurbit[8]uril the predominant product is that of dimerization. Such a change in product distribution is attributed to the localization of the olefins by the host cucurbit[8]uril. Most importantly, instead of a mixture of dimers, predominantly a single dimer was obtained in each case. The nature of the dimer that was formed could be rationalized on the basis of the principles of "best fit" and "minimization of electrostatic repulsion". The superior ability of cucurbit[8]uril compared to micelles to act as a templating agent is attributed to its ability to provide a reaction cavity that is tight and time-independent.

UR - http://www.scopus.com/inward/record.url?scp=34547164452&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34547164452&partnerID=8YFLogxK

U2 - 10.1021/la700803k

DO - 10.1021/la700803k

M3 - Article

C2 - 17539667

AN - SCOPUS:34547164452

VL - 23

SP - 7545

EP - 7554

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 14

ER -