Direct Observation of a Transiently Formed Isomer during Iodoform Photolysis in Solution by Time-Resolved X-ray Liquidography

Chi Woo Ahn; Hosung Ki; Joonghan Kim; Jeongho Kim; Sungjun Park; Yunbeom Lee; Kyung Hwan Kim; Qingyu Kong; Jiwon Moon; Martin Nors Pedersen; Michael Wulff; Hyotcherl Ihee

doi:10.1021/acs.jpclett.7b03125

Direct Observation of a Transiently Formed Isomer during Iodoform Photolysis in Solution by Time-Resolved X-ray Liquidography

Chi Woo Ahn
, Hosung Ki
, Joonghan Kim
, Jeongho Kim
, Sungjun Park
, Yunbeom Lee
, Kyung Hwan Kim
, Qingyu Kong
, Jiwon Moon
, Martin Nors Pedersen
, Michael Wulff
, Hyotcherl Ihee

Department of Chemistry

Korea Advanced Institute of Science and Technology
Institute for Basic Science
The Catholic University of Korea
Inha University
AlbaNova University Center
St Aubin BP48
European Synchrotron Radiation Facility

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

Photolysis of iodoform (CHI₃) in solution has been extensively studied, but its reaction mechanism remains elusive. In particular, iso-iodoform (iso-CHI₂-I) is formed as a product of the photolysis reaction, but its detailed structure is not known, and whether it is a major intermediate species has been controversial. Here, by using time-resolved X-ray liquidography, we determined the reaction mechanism of CHI₃ photodissociation in cyclohexane as well as the structure of iso-CHI₂-I. Both iso-CHI₂-I and CHI₂ radical were found to be formed within 100 ps with a branching ratio of 40:60. Iodine radicals (I), formed during the course of CHI₃ photolysis, recombine nongeminately with either CHI₂ or I. Based on our structural analysis, the I-I distance and the C-I-I angle of iso-CHI₂-I were determined to be 2.922 ± 0.004 Å and 133.9 ± 0.8°, respectively.

Original language	English
Pages (from-to)	647-653
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	9
Issue number	3
DOIs	https://doi.org/10.1021/acs.jpclett.7b03125
State	Published - 1 Feb 2018

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@article{06211c19d3004c53ac57feb87fbc0f9e,

title = "Direct Observation of a Transiently Formed Isomer during Iodoform Photolysis in Solution by Time-Resolved X-ray Liquidography",

abstract = "Photolysis of iodoform (CHI3) in solution has been extensively studied, but its reaction mechanism remains elusive. In particular, iso-iodoform (iso-CHI2-I) is formed as a product of the photolysis reaction, but its detailed structure is not known, and whether it is a major intermediate species has been controversial. Here, by using time-resolved X-ray liquidography, we determined the reaction mechanism of CHI3 photodissociation in cyclohexane as well as the structure of iso-CHI2-I. Both iso-CHI2-I and CHI2 radical were found to be formed within 100 ps with a branching ratio of 40:60. Iodine radicals (I), formed during the course of CHI3 photolysis, recombine nongeminately with either CHI2 or I. Based on our structural analysis, the I-I distance and the C-I-I angle of iso-CHI2-I were determined to be 2.922 ± 0.004 {\AA} and 133.9 ± 0.8°, respectively.",

author = "Ahn, \{Chi Woo\} and Hosung Ki and Joonghan Kim and Jeongho Kim and Sungjun Park and Yunbeom Lee and Kim, \{Kyung Hwan\} and Qingyu Kong and Jiwon Moon and Pedersen, \{Martin Nors\} and Michael Wulff and Hyotcherl Ihee",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/acs.jpclett.7b03125",

language = "English",

volume = "9",

pages = "647--653",

journal = "Journal of Physical Chemistry Letters",

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T1 - Direct Observation of a Transiently Formed Isomer during Iodoform Photolysis in Solution by Time-Resolved X-ray Liquidography

AU - Ahn, Chi Woo

AU - Ki, Hosung

AU - Kim, Joonghan

AU - Kim, Jeongho

AU - Park, Sungjun

AU - Lee, Yunbeom

AU - Kim, Kyung Hwan

AU - Kong, Qingyu

AU - Moon, Jiwon

AU - Pedersen, Martin Nors

AU - Wulff, Michael

AU - Ihee, Hyotcherl

PY - 2018/2/1

Y1 - 2018/2/1

N2 - Photolysis of iodoform (CHI3) in solution has been extensively studied, but its reaction mechanism remains elusive. In particular, iso-iodoform (iso-CHI2-I) is formed as a product of the photolysis reaction, but its detailed structure is not known, and whether it is a major intermediate species has been controversial. Here, by using time-resolved X-ray liquidography, we determined the reaction mechanism of CHI3 photodissociation in cyclohexane as well as the structure of iso-CHI2-I. Both iso-CHI2-I and CHI2 radical were found to be formed within 100 ps with a branching ratio of 40:60. Iodine radicals (I), formed during the course of CHI3 photolysis, recombine nongeminately with either CHI2 or I. Based on our structural analysis, the I-I distance and the C-I-I angle of iso-CHI2-I were determined to be 2.922 ± 0.004 Å and 133.9 ± 0.8°, respectively.

AB - Photolysis of iodoform (CHI3) in solution has been extensively studied, but its reaction mechanism remains elusive. In particular, iso-iodoform (iso-CHI2-I) is formed as a product of the photolysis reaction, but its detailed structure is not known, and whether it is a major intermediate species has been controversial. Here, by using time-resolved X-ray liquidography, we determined the reaction mechanism of CHI3 photodissociation in cyclohexane as well as the structure of iso-CHI2-I. Both iso-CHI2-I and CHI2 radical were found to be formed within 100 ps with a branching ratio of 40:60. Iodine radicals (I), formed during the course of CHI3 photolysis, recombine nongeminately with either CHI2 or I. Based on our structural analysis, the I-I distance and the C-I-I angle of iso-CHI2-I were determined to be 2.922 ± 0.004 Å and 133.9 ± 0.8°, respectively.

UR - https://www.scopus.com/pages/publications/85041445685

U2 - 10.1021/acs.jpclett.7b03125

DO - 10.1021/acs.jpclett.7b03125

M3 - Article

C2 - 29337571

AN - SCOPUS:85041445685

SN - 1948-7185

VL - 9

SP - 647

EP - 653

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 3

ER -

Direct Observation of a Transiently Formed Isomer during Iodoform Photolysis in Solution by Time-Resolved X-ray Liquidography

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