Molecular switch properties of 7-hydroxyquinoline compounds

András Csehi, G. Halász, A. Vibók

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The present study is concerned with the theoretical study of possible molecular switch systems. The 7-hydroxyquinoline-8-carboxamide molecule and its single-, double-, and triple-substituted derivatives are investigated with the aim of revealing characteristic switch features. Molecular switches can be considered as composed of a frame and a crane component. According to a recent study, the 7-hydroxyquinoline double-ring system constitutes the frame moiety, while a carboxamide group at position 8 plays the role of the crane part (Csehi et al., Phys. Chem. Chem. Phys. 2013, 15, 18048). The effect of single 2-,4-,6-methyl, double 2,4-, 2,6-diamino, and triple 2,4,6-triamino substitutions to the molecular frame has been investigated using high level ab initio techniques. As a possible reaction mechanism, excited state intramolecular hydrogen transfer mediated by the frame-crane torsion has been considered. At the terminal structures of this pathway, second-order approximate coupled-cluster (CC2) quality vertical excitation energies and oscillator strengths have been calculated for the three lowest-lying singlet electronic excited states of all the studied systems. Single point calculations at selected geometries of the reaction path were carried out at the CC2 level as well, while conical intersections (CIs) between the ground and first excited states near perpendicular twisted geometries were optimized using the complete active space self-consistent field method. To confirm the presence of CIs, nonadiabatic coupling terms have been derived and applying the topological line integral technique, the topological (or Berry) phase has been calculated surrounding the point of CI. The results of this work clearly demonstrate the fulfillment of several molecular switch properties by the investigated quinoline derivatives. An extensive comparison between the different compounds is presented as well.

Original languageEnglish
Pages (from-to)1135-1145
Number of pages11
JournalInternational Journal of Quantum Chemistry
Volume114
Issue number17
DOIs
Publication statusPublished - Sep 5 2014

Fingerprint

cranes
Cranes
switches
Switches
Excited states
intersections
excitation
Derivatives
Geometry
Excitation energy
quinoline
geometry
oscillator strengths
Torsional stress
torsion
self consistent fields
Hydrogen
Substitution reactions
substitutes
Molecules

Keywords

  • ab initio study
  • conical intersection
  • molecular switches
  • nonadiabatic coupling
  • quinoline compounds

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

Molecular switch properties of 7-hydroxyquinoline compounds. / Csehi, András; Halász, G.; Vibók, A.

In: International Journal of Quantum Chemistry, Vol. 114, No. 17, 05.09.2014, p. 1135-1145.

Research output: Contribution to journalArticle

@article{74dc23b937764154be4362113ff544a0,
title = "Molecular switch properties of 7-hydroxyquinoline compounds",
abstract = "The present study is concerned with the theoretical study of possible molecular switch systems. The 7-hydroxyquinoline-8-carboxamide molecule and its single-, double-, and triple-substituted derivatives are investigated with the aim of revealing characteristic switch features. Molecular switches can be considered as composed of a frame and a crane component. According to a recent study, the 7-hydroxyquinoline double-ring system constitutes the frame moiety, while a carboxamide group at position 8 plays the role of the crane part (Csehi et al., Phys. Chem. Chem. Phys. 2013, 15, 18048). The effect of single 2-,4-,6-methyl, double 2,4-, 2,6-diamino, and triple 2,4,6-triamino substitutions to the molecular frame has been investigated using high level ab initio techniques. As a possible reaction mechanism, excited state intramolecular hydrogen transfer mediated by the frame-crane torsion has been considered. At the terminal structures of this pathway, second-order approximate coupled-cluster (CC2) quality vertical excitation energies and oscillator strengths have been calculated for the three lowest-lying singlet electronic excited states of all the studied systems. Single point calculations at selected geometries of the reaction path were carried out at the CC2 level as well, while conical intersections (CIs) between the ground and first excited states near perpendicular twisted geometries were optimized using the complete active space self-consistent field method. To confirm the presence of CIs, nonadiabatic coupling terms have been derived and applying the topological line integral technique, the topological (or Berry) phase has been calculated surrounding the point of CI. The results of this work clearly demonstrate the fulfillment of several molecular switch properties by the investigated quinoline derivatives. An extensive comparison between the different compounds is presented as well.",
keywords = "ab initio study, conical intersection, molecular switches, nonadiabatic coupling, quinoline compounds",
author = "Andr{\'a}s Csehi and G. Hal{\'a}sz and A. Vib{\'o}k",
year = "2014",
month = "9",
day = "5",
doi = "10.1002/qua.24639",
language = "English",
volume = "114",
pages = "1135--1145",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",
number = "17",

}

TY - JOUR

T1 - Molecular switch properties of 7-hydroxyquinoline compounds

AU - Csehi, András

AU - Halász, G.

AU - Vibók, A.

PY - 2014/9/5

Y1 - 2014/9/5

N2 - The present study is concerned with the theoretical study of possible molecular switch systems. The 7-hydroxyquinoline-8-carboxamide molecule and its single-, double-, and triple-substituted derivatives are investigated with the aim of revealing characteristic switch features. Molecular switches can be considered as composed of a frame and a crane component. According to a recent study, the 7-hydroxyquinoline double-ring system constitutes the frame moiety, while a carboxamide group at position 8 plays the role of the crane part (Csehi et al., Phys. Chem. Chem. Phys. 2013, 15, 18048). The effect of single 2-,4-,6-methyl, double 2,4-, 2,6-diamino, and triple 2,4,6-triamino substitutions to the molecular frame has been investigated using high level ab initio techniques. As a possible reaction mechanism, excited state intramolecular hydrogen transfer mediated by the frame-crane torsion has been considered. At the terminal structures of this pathway, second-order approximate coupled-cluster (CC2) quality vertical excitation energies and oscillator strengths have been calculated for the three lowest-lying singlet electronic excited states of all the studied systems. Single point calculations at selected geometries of the reaction path were carried out at the CC2 level as well, while conical intersections (CIs) between the ground and first excited states near perpendicular twisted geometries were optimized using the complete active space self-consistent field method. To confirm the presence of CIs, nonadiabatic coupling terms have been derived and applying the topological line integral technique, the topological (or Berry) phase has been calculated surrounding the point of CI. The results of this work clearly demonstrate the fulfillment of several molecular switch properties by the investigated quinoline derivatives. An extensive comparison between the different compounds is presented as well.

AB - The present study is concerned with the theoretical study of possible molecular switch systems. The 7-hydroxyquinoline-8-carboxamide molecule and its single-, double-, and triple-substituted derivatives are investigated with the aim of revealing characteristic switch features. Molecular switches can be considered as composed of a frame and a crane component. According to a recent study, the 7-hydroxyquinoline double-ring system constitutes the frame moiety, while a carboxamide group at position 8 plays the role of the crane part (Csehi et al., Phys. Chem. Chem. Phys. 2013, 15, 18048). The effect of single 2-,4-,6-methyl, double 2,4-, 2,6-diamino, and triple 2,4,6-triamino substitutions to the molecular frame has been investigated using high level ab initio techniques. As a possible reaction mechanism, excited state intramolecular hydrogen transfer mediated by the frame-crane torsion has been considered. At the terminal structures of this pathway, second-order approximate coupled-cluster (CC2) quality vertical excitation energies and oscillator strengths have been calculated for the three lowest-lying singlet electronic excited states of all the studied systems. Single point calculations at selected geometries of the reaction path were carried out at the CC2 level as well, while conical intersections (CIs) between the ground and first excited states near perpendicular twisted geometries were optimized using the complete active space self-consistent field method. To confirm the presence of CIs, nonadiabatic coupling terms have been derived and applying the topological line integral technique, the topological (or Berry) phase has been calculated surrounding the point of CI. The results of this work clearly demonstrate the fulfillment of several molecular switch properties by the investigated quinoline derivatives. An extensive comparison between the different compounds is presented as well.

KW - ab initio study

KW - conical intersection

KW - molecular switches

KW - nonadiabatic coupling

KW - quinoline compounds

UR - http://www.scopus.com/inward/record.url?scp=84904462766&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84904462766&partnerID=8YFLogxK

U2 - 10.1002/qua.24639

DO - 10.1002/qua.24639

M3 - Article

VL - 114

SP - 1135

EP - 1145

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 17

ER -