TY - JOUR
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
N1 - Publisher Copyright:
© 2018 American Chemical Society.
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 - http://www.scopus.com/inward/record.url?scp=85041445685&partnerID=8YFLogxK
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 -