Searching for Improved Photoreleasing Abilities of Organic
Molecules

J 2015

Searching for Improved Photoreleasing Abilities of Organic Molecules

ŠOLOMEK, Tomáš, Hans Jakob WIRZ and Petr KLÁN

Basic information

Original name

Searching for Improved Photoreleasing Abilities of Organic Molecules

Authors

ŠOLOMEK, Tomáš (703 Slovakia, belonging to the institution), Hans Jakob WIRZ (756 Switzerland) and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)

Edition

Accounts of chemical research, American Chemical Society, 2015, 0001-4842

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 22.003

RIV identification code

RIV/00216224:14310/15:00081563

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/acs.accounts.5b00400

UT WoS

000366871400009

Keywords in English

photochemistry; photoremovable protecting groups; DFT calculations

Abstract

V originále

Photoremovable protecting groups (PPGs) are chemical auxiliaries that provide spatial and temporal control over the release of various molecules: bioagents (neurotransmitters and cell-signaling molecules, Ca2+ ions), acids, bases, oxidants, insecticides, pheromones, fragrances, etc. A major challenge for the improvement of PPGs lies in the development of organic chromophores that release the desired bioagents upon continuous irradiation at wavelengths above 650 nm, that is, in the tissue-transparent window. Understanding of the photorelease reaction mechanisms, investigated by laser flash photolysis and rationalized with the aid of quantum chemical calculations, allows for achieving this goal. In particular, simple Hiickel calculations provide useful guidelines for designing new PPGs, because both the lowest excited singlet and triplet states of conjugated systems can be reasonably well described by a single electronic configuration formed by promotion of a single electron from the highest occupied molecular orbital (HOMO) to the lowest unoccupied MO (LUMO) of the ground state configuration. Here we show that Hiickel calculations permit rapid identification of common features in the nodal properties of the frontier orbitals of various chromophores that can be classified into distinct chromophore families. If the electronic excitation involves a substantial electron density transfer to an sp(2) carbon atom at which HOMO and LUMO are nearly disjoint, for example, by virtue of symmetry, favorable photoheterolysis can be expected when the corresponding atom carries a leaving group at the alpha-position. We show examples of photoheterolytic reactions that indicate that the efficiency of photoheterolysis diminishes for chromophores absorbing in the NIR region. We provide a rationale for more efficient photoheterolytic reactions occurring via the triplet state, and we demonstrate the advantages of this mechanistic pathway. Analogies in the structure reactivity relationships of PPGs can therefore lead to new strategies for the development of more efficient NIR-absorbing photoremovable protecting groups.

Links

GA13-25775S, research and development project

Name: Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

Investor: Czech Science Foundation

LM2011028, research and development project

Name: RECETOX ? Národní infrastruktura pro výzkum toxických látek v prostředí

Investor: Ministry of Education, Youth and Sports of the CR

LO1214, research and development project

Name: Centrum pro výzkum toxických látek v prostředí (Acronym: RECETOX)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

ŠOLOMEK, Tomáš, Hans Jakob WIRZ and Petr KLÁN. Searching for Improved Photoreleasing Abilities of Organic Molecules. Accounts of chemical research. American Chemical Society, 2015, vol. 48, No 12, p. 3064-3072. ISSN 0001-4842. Available from: https://dx.doi.org/10.1021/acs.accounts.5b00400.

@article{1335094,
   author = {Šolomek, Tomáš and Wirz, Hans Jakob and Klán, Petr},
   article_number = {12},
   doi = {http://dx.doi.org/10.1021/acs.accounts.5b00400},
   keywords = {photochemistry; photoremovable protecting groups; DFT calculations},
   language = {eng},
   issn = {0001-4842},
   journal = {Accounts of chemical research},
   title = {Searching for Improved Photoreleasing Abilities of Organic Molecules},
   url = {http://pubs.acs.org/doi/10.1021/acs.accounts.5b00400},
   volume = {48},
   year = {2015}
}

TY  - JOUR
ID  - 1335094
AU  - Šolomek, Tomáš - Wirz, Hans Jakob - Klán, Petr
PY  - 2015
TI  - Searching for Improved Photoreleasing Abilities of Organic Molecules
JF  - Accounts of chemical research
VL  - 48
IS  - 12
SP  - 3064-3072
EP  - 3064-3072
PB  - American Chemical Society
SN  - 00014842
KW  - photochemistry
KW  - photoremovable protecting groups
KW  - DFT calculations
UR  - http://pubs.acs.org/doi/10.1021/acs.accounts.5b00400
L2  - http://pubs.acs.org/doi/10.1021/acs.accounts.5b00400
N2  - Photoremovable protecting groups (PPGs) are chemical auxiliaries that provide spatial and temporal control over the release of various molecules: bioagents (neurotransmitters and cell-signaling molecules, Ca2+ ions), acids, bases, oxidants, insecticides, pheromones, fragrances, etc. A major challenge for the improvement of PPGs lies in the development of organic chromophores that release the desired bioagents upon continuous irradiation at wavelengths above 650 nm, that is, in the tissue-transparent window. Understanding of the photorelease reaction mechanisms, investigated by laser flash photolysis and rationalized with the aid of quantum chemical calculations, allows for achieving this goal. In particular, simple Hiickel calculations provide useful guidelines for designing new PPGs, because both the lowest excited singlet and triplet states of conjugated systems can be reasonably well described by a single electronic configuration formed by promotion of a single electron from the highest occupied molecular orbital (HOMO) to the lowest unoccupied MO (LUMO) of the ground state configuration. Here we show that Hiickel calculations permit rapid identification of common features in the nodal properties of the frontier orbitals of various chromophores that can be classified into distinct chromophore families. If the electronic excitation involves a substantial electron density transfer to an sp(2) carbon atom at which HOMO and LUMO are nearly disjoint, for example, by virtue of symmetry, favorable photoheterolysis can be expected when the corresponding atom carries a leaving group at the alpha-position. We show examples of photoheterolytic reactions that indicate that the efficiency of photoheterolysis diminishes for chromophores absorbing in the NIR region. We provide a rationale for more efficient photoheterolytic reactions occurring via the triplet state, and we demonstrate the advantages of this mechanistic pathway. Analogies in the structure reactivity relationships of PPGs can therefore lead to new strategies for the development of more efficient NIR-absorbing photoremovable protecting groups.
ER  -

ŠOLOMEK, Tomáš, Hans Jakob WIRZ and Petr KLÁN. Searching for Improved Photoreleasing Abilities of Organic Molecules. \textit{Accounts of chemical research}. American Chemical Society, 2015, vol.~48, No~12, p.~3064-3072. ISSN~0001-4842. Available from: https://dx.doi.org/10.1021/acs.accounts.5b00400.

Detailed Information on Publication Record