Remarkable static and dynamic nonlinear optical responses of Al₁₃-TCNQ/F4-TCNQ complexes: a quantum chemical study

Abstract

Al13-TCNQ/F4-TCNQ complexes, which exhibit excellent stability and first hyperpolarizabilities, can be considered as candidates for UV and IR NLO materials.

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al13 and Dianhydrides

“…As given in Table , the NPA analysis shows that the dianhydride unit exhibits a negative charge (−1.387, −0.599, and −0.578 | e |) due to the intrinsic electron-withdrawing ability. This suggests that the Al 13 fragment acts as an electron donor in the complex, which is similar to the case of the Al 13 -TCNQ and Al 13 –F4-TCNQ complexes . For Al 13 –PMDA, the positive charges on the two Al atoms connected to the O atoms are +0.919 and +0.770 | e |, the O atoms have a negative charge of −0.877 and −0.866 | e |, respectively, and the charge of the centered Al atom in Al 13 is −1.437 | e |.…”

“…This suggests that the Al 13 fragment acts as an electron donor in the complex, which is similar to the case of the Al 13 -TCNQ and Al 13 −F4-TCNQ complexes. 39 For Al 13 −PMDA, the positive charges on the two The NLO properties of all complexes have been explored by calculating mean polarizabilities (α 0 ) and first hyperpolarizabilities (β 0 ) as given in Table 3. The polarizability of Al 13 is 517 au at CAM-B3LYP/6-31+G(d) level and 512 au at M06/ 6-31+G(d) level.…”

“…It was observed that Al 13 X (X = Li, Na, and K) and M 3 O–Al 13 (M = Li, Na, and K) complexes have larger β 0 of 2.17 × 10 3 to 1.55 × 10 4 au. , The static β 0 values of novel superatomic molecules [Al 13 (CNC 6 H 4 NC)PAl 12 and Al 13 (CNC 6 H 4 NC)CAl 12 ] were calculated to be 15.43 × 10 4 au and 59.74 × 10 4 au, respectively . Additionally, Al 13 can act as an electron donor when Al clusters interact with strong electron-withdrawing groups. , We designed stable potential candidate NLO molecules by combining an Al 13 cluster with a TCNQ/F4-TCNQ electron acceptor . Undoubtedly, these achievements clearly show the unlimited potential of the Al 13 cluster in creating Al 13 -organic molecule models with excellent second-order NLO properties.…”

“…35,36 37 Additionally, Al 13 can act as an electron donor when Al clusters interact with strong electron-withdrawing groups. 38,39 We designed stable potential candidate NLO molecules by combining an Al 13 cluster with a TCNQ/F4-TCNQ electron acceptor. 39 Undoubtedly, these achievements clearly show the unlimited potential of the Al 13 cluster in creating Al 13 -organic molecule models with excellent secondorder NLO properties.…”