Metal Ions Play Different Roles in the Third‐Order Nonlinear Optical Properties of d¹⁰ Metal–Organic Clusters

Abstract

Research into nonlinear optical (NLO) materials has become increasingly intensive because of their potential applications in optical fibers, data storage, optical computing, image processing, optical switching, and optical limiting.[1] Thus, the design and synthesis of new materials with large NLO capability represents an active field in modern chemistry, physics, and materials science.[2] Metal clusters are reported to be excellent candidates for NLO materials [3] since they involve dp-pp delocalized systems and dp-dp conjugated systems.[4] These compounds have a large variety of structures and diverse electronic properties that can be tuned by virtue of the coordinated metal; [5] thus the opportunity exists to tune the NLO properties of metal complexes. Metal clusters can also extend the p-conjugated length, which is one of the many methods used to increase molecular NLO susceptibility c (3) values. Moreover, the NLO properties of metal clusters can be enhanced by the introduction of metal!ligand and ligand!metal charge-transfer states.[6] Although many methods can be used to promote the NLO properties of metal clusters, the origination of the NLO properties is the delocalization of the p-electron cloud. [7] This delocalization in metal clusters is mainly brought about by metal ions constructing the skeleton and organic ligands fixing the skeleton, thus both the metal ions and the organic ligands should be important for the nonlinear optical properties of the clusters. To the best of our knowledge, however, all studies confirm that heavy-metal ions play very important roles on the third-order NLO properties of metal clusters because their incorporation introduces more sublevels into the energy hierarchy, which permits more allowed electronic transitions to take place and hence a larger NLO effect to be produced.

A new single pot synthesis of μ-bis(oxido)bis{oxidovanadium(V)} dipicolinato complex with 2-aminopyridinium as counter cation: Spectroscopic, structural, catalytic and theoretical studies

“…Fine), cis-cyclooctene (Aldrich), t-butyl hydroperoxide (Fluka) were procured and used as received. 2,6-dicarboxamido-2-pyridylpyridine (H 2 dcapp) was prepared and purified following the literature procedure [28].…”

Diversified architectures of one-dimensional zinc(II) and cadmium(II) coordination polymers incorporating bipyridyl ligands: Syntheses, structures, theoretical studies, fluorescent and nonlinear optical properties

“…On the other hand, d 10 metal (such as Cu(I), Ag(I), Au(I), Zn(II) and Cd(II)) CPs have attracted extensive interest in recent years due to their intriguing structures [30,31], wide variety of geometries, many different coordination numbers and potential optical applications in fluorescence [13,14,31] and nonlinear optics (NLO) [32,33]. A particularly promising class of ligands is represented by molecules containing two pyridyl donor units interconnected by chains or groups of different types.…”

Two manganese(II) complexes based on anthracene-9-carboxylate: Syntheses, crystal structures, and magnetic properties

“…The effective and facile approach for the synthesis of such complexes is still the appropriate choice of well-designed organic ligands as bridges or terminal groups (building blocks) with metal ions or metal clusters as nodes. So far, this has been at an evolutionary stage with the current focus mainly on understanding the factors that determine the crystal packing as well as exploring relevant properties [3,[7][8][9][10][11]. Among various ligands, the versatile carboxylic acid ligands exhibiting diverse coordination modes, especially benzene-based and naphthalene-based carboxylic acids have been employed and well documented in the preparations of various carboxylato-containing Mn II metalorganic complexes [12][13][14][15][16][17][18][19][20][21][22].…”

“…Over the past decades, the rational design and synthesis of functional coordination architectures have attracted great interest because of not only their intriguing structures but also their potential uses as functional materials [1][2][3][4][5][6][7][8][9][10][11]. The effective and facile approach for the synthesis of such complexes is still the appropriate choice of well-designed organic ligands as bridges or terminal groups (building blocks) with metal ions or metal clusters as nodes.…”