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

• Published in: Journal of molecular modeling 2019-08, Vol.25 (8), p.212-212, Article 212
• Main Authors: Arif, Ali Muhammad, Yousaf, Afifa, Zhong, Rong-Lin, Akhtar, Mansoor, Muhammad, Shabbir, Xu, Hong-liang, Su, Zhong-Min
• Format: Article
• Language: English
• Subjects: Alkali metals; Alkaline earth metals; Calcium ions; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Coordination compounds; Coumarin; Derivatives; Ions; Lithium; Mathematical analysis; Metal ions; Molecular machines; Molecular Medicine; Nonlinear optics; Nonlinear response; Optical properties; Original Paper; Rayleigh scattering; Spiropyrans; Switches; Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-019-4068-6

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 Ca 2+ ), 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