Nanoclusters such as Al[Formula: see text]N[Formula: see text] have received increased attention due to their diverse applications in the fields of optoelectronics and energy storage. In this paper, we have investigated a series of alkaline earth metal (AEM)-encapsulated Al[Formula: see text]N[Formula: see text] nanoclusters for hydrogen adsorption. Thermodynamic adsorption parameters, optical and nonlinear optical properties were investigated using density functional theory (DFT) at the B3LYP/6-31G(d,p) level of theory. Encapsulation of AEMs (Be, Mg and Ca) is an effective strategy to improve the NLO reaction and thermodynamic and adsorption properties of Al[Formula: see text]N[Formula: see text] nanoclusters. The adsorption energies ranging from [Formula: see text]26.57[Formula: see text]kJ/mol to [Formula: see text]213.33[Formula: see text]kJ/mol for the three guests (Be, Mg and Ca) capsulated Al[Formula: see text]N[Formula: see text] nanoclusters are observed. The adsorption energy is affected by the size of the nanocage. Therefore, Ca- and Mg-encapsulated cages show higher values of adsorption energy. Overall, an increase in adsorption energy ([Formula: see text][Formula: see text]kJ/mol to [Formula: see text]91.06[Formula: see text]kJ/mol) is observed for (Be, Mg and Ca) encapsulated Al[Formula: see text]N[Formula: see text] nanoclusters compared to untreated Al[Formula: see text]N[Formula: see text] and H2-Al[Formula: see text]N[Formula: see text] cages. Moreover, adsorption of hydrogen on AEMs encapsulated in Al[Formula: see text]N[Formula: see text] leads to a decrease in the HOMO-LUMO energy gap with an enhancement of linear and nonlinear hyperpolarizability. All hydrogen-adsorbed AEMs Al[Formula: see text]N[Formula: see text] nanocages exhibit large [Formula: see text] and [Formula: see text] values, suggesting that these systems are potential candidates for optical materials. Various geometrical parameters such as frontier molecular orbitals (FMOs), partial density of states, global quantum descriptor of reactivity, natural bond orbital testing and molecular electrostatic strength analyses were performed to investigate the thermodynamic stability of all the studied systems. The results obtained confirmed that the designed systems are suitable for hydrogen storage. Therefore, we recommend that these systems be investigated for their hydrogen storage and optical properties.

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Herein, we report the synthesis of an unsymmetrical diruthenium bridging unit containing a multidentate oxamate ligand and the subsequent formation of a rectangular supramolecule. The reaction of oxamate 1, 2-((4-bromo-2,6dimethylphenyl)amino)-2-oxo-acetic acid, and [(p-cymene)RuCl 2 ] 2 affords a novel unsymmetrical diruthenium acceptor clip 2, where two ruthenium metal centers are ligated with either [O,O] or [N,O].The molecular clip 2 and bipyridine donor selfassemble to form two-dimensional rectangular supramolecule 3. Self-assembly can produce seven possible isomers depending on the position of the substituted bromoaryl groups. However, 1 H NMR spectroscopic investigation indicated only two different isomers in the reaction mixture. A single isomer is isolated via crystallization, and X-ray crystallography confirms that the product is a C 1 symmetric two-dimensional rectangular supramolecule, in which two bromoaryl groups are located in the farthest position from each other. Theoretical calculations suggest that the self-assembly of supramolecule 3 occurred via 1:1 adducts of the diruthenium molecular clip and bipyridine as an intermediate to predominantly form a single isomer.

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