Metal ions doped into merocyanine form of coumarin derivatives: nonlinear optical molecular switches

  • Ali Muhammad Arif
  • Afifa Yousaf
  • Rong-Lin Zhong
  • Mansoor Akhtar
  • Shabbir Muhammad
  • Hong-liang XuEmail author
  • Zhong-Min SuEmail author
Original Paper


In the present study, DFT calculations are carried out on domestically designed 7-methyl-2-phenyl-5’H-spiro[chromene-4,2′-chromeno[3,4-e][1,3]oxazin]-5′-one spiropyran and merocyanine derivatives to recognize alkali and alkaline earth metal ions. Detection of these metal ions can be attained by exploiting the variation of the second-order nonlinear optical properties. Merocyanine forms of these derivatives exhibit the ability to complex with different metal ions (Li+, Na+, K+, and Ca2+), which is associated with large contrasts in the hyper-Rayleigh scattering (HRS) response as a function of metal size and charge. Interestingly, in this study, Mero-Li+ shows significant nonlinear optical response with dynamic HRS first hyperpolarizability amounting to 7607 a.u., which is about nine times higher than its corresponding spiro form (846 a.u.) at the CAM-B3LYP/6-311G* level of theory. The present investigation clarifies the effect of metal nature on the enhancement of the first hyperpolarizability between the closed and open forms of the studied coumarin derivatives.

Graphical abstract

The coumarin-based compound 3 demonstrate the higher second-order NLO responses as a function of metal cation size and charges. Complexation of smaller alkali metal ions leads to the formation of stronger metal-ligand bonds, larger geometrical relaxations and significant enhancement of the HRS first hyperpolarizabilities. This present investigation elucidates the effect of metal nature on the enhancement of the first hyperpolarizability between the closed and open forms of studied coumarin derivatives


First hyperpolarizability Molecular switches Merocyanine Metal doping NLO 



H-L Xu acknowledges support for the project funded by the China Postdoctoral Science Foundation (2014 M560227) and the Fundamental Research Funds for the Central Universities 2412018ZD008. S Muhamma d at the King Khalid University is thankful to the Deanship of Scientific Research at King Khalid University for funding this work through Research Group Project under grant number (R. G. P.1/165/40).

Compliance with ethical standards

Conflict of interest

There are no conflicts to declare.

Supplementary material

894_2019_4068_MOESM1_ESM.docx (84 kb)
ESM 1 (DOCX 84 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute of Functional Material Chemistry, Faculty of ChemistryNortheast Normal UniversityJilinPeople’s Republic of China
  2. 2.Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical ChemistryJilin UniversityJilinPeople’s Republic of China
  3. 3.Department of Physics, College of ScienceKing Khalid UniversityAbhaSaudi Arabia
  4. 4.School of Chemistry and Environmental EngineeringChangchun University of Science and TechnologyJilinPeople’s Republic of China

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