Interplay among aromaticity, magnetism, and nonlinear optical response in all-metal aromatic systems.

All-metal aromatic molecules are the latest inclusion in the family of aromatic systems. Two different classes of all-metal aromatic clusters are primarily identified: one is aromatic only in the low spin state, and the other shows aromaticity even in high-spin situations. This observation prompts us to investigate the effect of spin multiplicity on aromaticity, taking Al(4)(2-), Te(2)As(2)(2-), and their copper complexes as reference systems. Among these clusters, it has been found that the molecules that are aromatic only in their singlet state manifest antiaromaticity in their triplet state. The aromaticity in the singlet state is characterized by the diatropic ring current circulated through the bonds, which are cleaved to generate excess spin density on the atoms in the antiaromatic triplet state. Hence, in such systems, an antagonistic relationship between aromaticity and high-spin situations emerges. On the other hand, in the case of triplet aromatic molecules, the magnetic orbitals and the orbitals maintaining aromaticity are different; hence, aromaticity is not depleted in the high-spin state. The nonlinear optical (NLO) behavior of the same set of clusters in different spin states has also been addressed. We correlate the second hyperpolarizability and spin density in order to judge the effect of spin multiplicity on third-order NLO response. This correlation reveals a high degree of NLO behavior in systems with excess spin density. The variance of aromaticity and NLO response with spin multiplicity is found to stem from a single aspect, the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), and eventually the interplay among aromaticity, magnetism, and NLO response in such materials is established. Hence, the HOMO-LUMO energy gap becomes the cornerstone for tuning the interplay. This correlation among the said properties is not system-specific and thus can be envisaged even beyond the periphery of all-metal aromatic clusters. Such interplay is of crucial importance in tailoring novel paradigm of multifunctional materials.