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@article{1407991,
author = {Slanina, Tomáš and Shrestha, Pradeep and Palao Utiel, Eduardo and Kand, Dnyaneshwar and Peterson, Julie A. and Dutton, Andrew S. and Rubinstein, Naama and Weinstain, Roy and Winter, Arthur H. and Klán, Petr},
article_location = {WASHINGTON},
article_number = {42},
doi = {http://dx.doi.org/10.1021/jacs.7608532},
keywords = {P-HYDROXYPHENACYL; VISIBLE-LIGHT; CAGED GABA; REACTION-MECHANISMS; STOKES SHIFT; GREEN LIGHT; DYES; DERIVATIVES; ATP; PHOTOCHEMISTRY},
language = {eng},
issn = {0002-7863},
journal = {Journal of the American Chemical Society},
title = {In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups},
volume = {139},
year = {2017}
}
TY - JOUR
ID - 1407991
AU - Slanina, Tomáš - Shrestha, Pradeep - Palao Utiel, Eduardo - Kand, Dnyaneshwar - Peterson, Julie A. - Dutton, Andrew S. - Rubinstein, Naama - Weinstain, Roy - Winter, Arthur H. - Klán, Petr
PY - 2017
TI - In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
JF - Journal of the American Chemical Society
VL - 139
IS - 42
SP - 15168-15175
EP - 15168-15175
PB - American Chemical Society
SN - 00027863
KW - P-HYDROXYPHENACYL
KW - VISIBLE-LIGHT
KW - CAGED GABA
KW - REACTION-MECHANISMS
KW - STOKES SHIFT
KW - GREEN LIGHT
KW - DYES
KW - DERIVATIVES
KW - ATP
KW - PHOTOCHEMISTRY
N2 - A detailed investigation of the photophysical parameters and photochemical reactivity of meso-methyl BODIPY photoremovable protecting groups was accomplished through systematic variation of the leaving group (LG) and core substituents as well as substitutions at boron. Efficiencies of the LG release were evaluated using both steady-state and transient absorption spectroscopies as well as computational analyses to identify the optimal structural features. We find that the quantum yields for photorelease with this photocage are highly sensitive to substituent effects. In particular, we find that the quantum yields of photorelease are improved with derivatives with higher intersystem crossing quantum yields, which can be promoted by core heavy atoms. Moreover, release quantum yields are dramatically improved by boron alkylation, whereas alkylation in the meso-methyl position has no effect. Better LGs are released considerably more efficiently than poorer LGs. We find that these substituent effects are additive, for example, a 2,6-diiodo-B-dimethyl BODIPY photocage features quantum yields of 28% for the mediocre LG acetate and a 95% quantum yield of release for chloride. The high chemical and quantum yields combined with the outstanding absorption properties of BODIPY dyes lead to photocages with uncaging cross sections over 10 000 M-1 cm(-1), values that surpass cross sections of related photocages absorbing visible light. These new photo cages, which absorb strongly near the second harmonic of an Nd:YAG laser (532 nm), hold promise for manipulating and interrogating biological and material systems with the high spatiotemporal control provided by pulsed laser irradiation, while avoiding the phototoxicity problems encountered with many UV-absorbing photocages. More generally, the insights gained from this structure reactivity relationship may aid in the development of new highly efficient photoreactions.
ER -
SLANINA, Tomáš, Pradeep SHRESTHA, Eduardo PALAO UTIEL, Dnyaneshwar KAND, Julie A. PETERSON, Andrew S. DUTTON, Naama RUBINSTEIN, Roy WEINSTAIN, Arthur H. WINTER and Petr KLÁN. In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups. \textit{Journal of the American Chemical Society}. WASHINGTON: American Chemical Society, 2017, vol.~139, No~42, p.~15168-15175. ISSN~0002-7863. Available from: https://dx.doi.org/10.1021/jacs.7608532.
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