Continuous studies are being carried out to explore new methods and carrier surfaces for target drug delivery. Herein, we report the covalent triazine framework C₆N₆ as a drug delivery carrier for fluorouracil (FU) and nitrosourea (NU) anti-cancer drugs. FU and NU are physiosorbed on C₆N₆ with adsorption energies of −28.14 kcal/mol and −27.54 kcal/mol, respectively. The outcomes of the non-covalent index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses reveal that the FU@C₆N₆ and NU@C₆N₆ complexes were stabilized through van der Waals interactions. Natural bond order (NBO) and electron density difference (EDD) analyses show an appreciable charge transfer from the drug and carrier. The FU@C₆N₆ complex had a higher charge transfer (−0.16 e⁻) compared to the NU@C₆N₆ complex (−0.02 e⁻). Frontier molecular orbital (FMO) analysis reveals that the adsorption of FU on C₆N₆ caused a more pronounced decrease in the HOMO-LUMO gap (E_H-L) compared to that of NU. The results of the FMO analysis are consistent with the NBO and EDD analyses. The drug release mechanism was studied through dipole moments and pH effects. The highest decrease in adsorption energy was observed for the FU@C₆N₆ complex in an acidic medium, which indicates that FU can easily be off-loaded from the carrier (C₆N₆) to a target site because the cancerous cells have a low pH compared to a normal cell. Thus, it may be concluded that C₆N₆ possesses the therapeutic potential to act as a nanocarrier for FU to treat cancer. Furthermore, the current study will also provide motivation to the scientific community to explore new surfaces for drug delivery applications.

Significant efforts are continuously exerted by the scientific community to explore new strategies to design materials with high nonlinear optical responses. An effective approach is to design alkalides based on Janus molecules. Herein, we present a new approach to remarkably boost the NLO response of alkalides by stacking the Janus molecules. Alkalides based on stacked Janus molecule, M-n-M' (where n = 2 & 3 while M and M′ are Li/Na/K) are studied for structural, energetic, electrical, and nonlinear optical properties. The thermodynamic stability of the designed complexes is confirmed by the energetic stabilities, which range between -14.07 and -28.77 kcal/mol. The alkalide character of alkali metals-doped complexes is confirmed by the NBO charge transfer and HOMO(s) densities. The HOMO densities are located on the doped alkali metal atoms, indicating their alkalide character. The absorptions in UV–Vis and near IR region confirm the deep ultraviolet transparency of the designed complexes. The maximum first static and dynamic hyperpolarizabilities of 5.13 × 10⁷ and 6.6 × 10⁶ au (at 1339 nm) confirm their high NLO response, especially for K-2-M′ complexes. The NLO response of alkalides based on stacked Janus molecules is 1–2 orders of magnitude higher than the alkalide based on Janus monomer. The high values of dc-Kerr and electric field-induced response e.g., max ∼10⁷ and 10⁸ au, respectively have been obtained. These findings suggest that our designed complexes envision a new insight into the rational design of stable high NLO performance materials.

Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10⁻¹⁷ cm²/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics.

Electronic and nonlinear optical properties of endohedral metallofullerenes are presented. The endohedral metallofullerenes contain transition metal encapsulated in inorganic fullerenes X₁₂Y₁₂ (X = B, Al & Y = N, P). The endohedral metallofullerenes (endo-TM@X₁₂Y₁₂) possess quite interesting geometric and electronic properties, which are the function of the nature of the atom and the size of fullerene. NBO charge and frontier molecular orbital analyses reveal that the transition metal encapsulated Al₁₂N₁₂ fullerenes (endo-TM@Al₁₂N₁₂) are true metalides when the transition metals are Ni, Cu and Zn. Endo-Cr@Al₁₂N₁₂ and endo-Co@Al₁₂N₁₂ are at the borderline between metalides and electrides with predominantly electride characteristics. The other members of the series are excess electron systems, which offer interesting electronic and nonlinear optical properties. The diversity of nature possessed by endo-TM@Al₁₂N₁₂ is not prevalent for other fullerenes. Endo-TM@Al₁₂P₁₂ are true metalides when the transition metals are (Cr-Zn). HOMO-LUMO gaps (E_H-L) are reduced significantly for these endohedral metallofullerenes, with a maximum percent decrease in E_H-L of up to 70%. Many complexes show odd–even oscillating behavior for E_H-L and dipole moments. Odd electron species contain large dipole moments and small E_H-L, whereas even electron systems have the opposite behavior. Despite the decrease in E_H-L, these systems show high kinetic and thermodynamic stabilities. The encapsulation of transition metals is a highly exergonic process. These endo-TM@X₁₂Y₁₂ possess remarkable nonlinear optical response in which the first hyperpolarizability reaches up to 2.79 × 10⁵ au for endo-V@Al₁₂N₁₂. This study helps in the comparative analysis of the potential nonlinear optical responses of electrides, metalides and other excess electron systems. In general, the potential nonlinear optical response of electrides is higher than metalides but lower than those of simple excess electron compounds. The higher non-linear optical response and interesting electronic characteristics of endo-TM@Al₁₂N₁₂ complexes may be promising contenders for potential NLO applications.