Synthesis and Characterization of a Dysprosium(III)–Iron(III) Heterodinuclear Complex: Crystallographic, Hirshfeld Surface, Density-Functional Theory, and Luminescence Analyses

Abstract

Here, a new cyano-bridged 3d–4f compound, a Dy(III)–Fe(III) molecular assembly ([Dy(DMF)4(H2O)3(μ-CN)Fe(CN)5.H2O] (1)), having a structure consisting of neutral one-dimensional (1D) chains, as well as an unbound aqua molecule, was synthesized and characterized using single crystal X-ray diffraction (XRD), infrared (IR), and elemental analyses. We then examined its structural topologies and studied its density functional theory (DFT), Hirshfeld surface analyses, and photophysical properties. The 1D chains were further linked by H-bond interactions, generating a three-dimensional (3D) motif which stabilizes the whole molecule. The weak interactions in 1 were assessed using Hirshfeld surface analyses, as well as fingerprint plots and DFT studies. Additionally, Hirshfeld surface analysis was performed to elucidate the roles of the weak interactions, such as the H⋯H, C⋯H, C–H⋯π, and van der Waals (vdW) interactions which are pivotal to stabilizing the crystal environment. Furthermore, the DFT studies were used to elucidate the bonding structure within the complex system. Complex 1 exhibits characteristic fluorescence as the Dy(III) complex is an excellent lime green luminescent material. Thus, it is considered to be a suitable material for preparing photoluminescent material.

Synthesis and Experimental Structure of a Multifunctional Catechol‐Azomethinebenzoic Acid, DFT/DMol3 Calculations, and Molecular Docking with Hsp90

“…The Hirshfeld surface and fingerprint plots for 1 are very similar to those for the recently reported ( E )‐4‐((2‐hydroxy‐3,5‐diiodobenzylidene)amino)benzoic acid (DHBA), [21] the 4‐methoxybenzyl‐2‐dihydroxybenzalaldimine ligand in a Zn coordination polymer, [8] and the (3‐((2‐hydroxy‐5‐nitrobenzylidene)amino)benzoic acid ligand in the complex [Cu 2 (L) 2 (Py) 4 ] [9] . This confirms our choice for the functional groups on 1 .…”

“…Density functional theory (DFT)‐calculated metrics agree very well with the experimental data (Table 1). The same planar trans configured molecular conformation was previously found in the crystal structure of the solvate DHBA⋅DMSO (DHBA= ( E )‐4‐((2‐hydroxy‐3,5‐diiodobenzylidene)amino)benzoic acid; DMSO=dimethyl sulfoxide), [21] and the 4‐methoxybenzyl‐2‐dihydroxybenzalaldimine units of a recently reported Zn coordination polymer [8] …”

“…Diaryl‐imines formed from 2‐hydroxybenzaldehyde and anilines provide a chelate N imine ^O phenolate binding and have been extensively studied [1,2,4,5,7–15] . including many examples of 2,3‐dihydroxybenzaldehyde derivatives [16–20] .…”

“…including many examples of 2,3‐dihydroxybenzaldehyde derivatives [16–20] . When including additionally to the 2,3‐dihydroxybenzaldehyde, the 4‐aminobenzoic acid functionality, the total number of studies is far smaller [8,12,21–25] . Some of them provide two carboxylic acid functions and vary in the location of the two phenolic OH group for building up hydrogen bonding networks [8,9,12,14,21] .…”

“…When including additionally to the 2,3‐dihydroxybenzaldehyde, the 4‐aminobenzoic acid functionality, the total number of studies is far smaller [8,12,21–25] . Some of them provide two carboxylic acid functions and vary in the location of the two phenolic OH group for building up hydrogen bonding networks [8,9,12,14,21] . The deprotonated function of such 2,3‐dihydroxybenzaldehyde‐4‐aminobenzoic acid derivatives was previously used for coordination of metals, [8,12] and contain the biologically important catechol (benzene‐1,2‐diol) unit [26–28] …”