Experimental and Theoretical Survey of Intramolecular Spodium Bonds/�/�-Holes and Noncovalent Interactions in Trinuclear Zn(II)-Salen Type Complex with OCN- Ions: A Holistic View in Crystal Engineering

Majumdar, D and Frontera, A and Roy, S and Sutradhar, D (2024) Experimental and Theoretical Survey of Intramolecular Spodium Bonds/�/�-Holes and Noncovalent Interactions in Trinuclear Zn(II)-Salen Type Complex with OCN- Ions: A Holistic View in Crystal Engineering. In: ACS Omega, 9 (1). pp. 1786-1797.

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Abstract

In this work, one new centrosymmetric trinuclear Zn(II) complex 1, {(OCN)Zn(L)}2Zn, using a salen-type ligand (H2L) in the presence of OCN- was synthesized and characterized via elemental, spectral, SEM-EDX, and single-crystal X-ray diffraction (SCXRD) study. In 1, SCXRD reveals two different stereochemical environments of zinc metal ions; one terminal Zn(II) center adopts square pyramidal geometries with the Addison parameter (�) 0.095, and the central Zn(II) is tetracoordinated tetrahedral geometry. This article provides evidence of the significance and presence of spodium bonds (SpBs) in solid-state crystal structures involving a pseudotetrahedral environment of the central Zn-atom. X-ray structures reveal intramolecular Zn···O SpBs caused by the methoxy (-OCH3) substituent O-atom adjacent to the coordinated phenoxy O-atom. These noncovalent interactions have been thoroughly studied using density functional theory calculations at the RI-BP862-D33/def2-TZVP level of theory that characterizes the nature of SpBs, including the Baders quantum theory of atoms-in-molecules �QTAIM�, molecular electrostatic potential (MEP) surface, and noncovalent index plot (NCI). In addition, a unique complex-isomer-based theoretical model has been vividly employed to estimate the SpBs energy in the complex. Natural bond orbital (NBO) analysis also tries to establish the differentiation between �-hole and �-hole SpBs� natures more authentically. The complex energy frameworks were used to investigate noncovalent interactions. To better understand the different intermolecular interactions, we conducted a Hirshfeld surface, which revealed N···H (15.4%) and O···H (9.1%) contacts and Zn···O (5.1%) (SpBs). © 2023 The Authors. Published by American Chemical Society.

Item Type:	Journal Article
Publication:	ACS Omega
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society
Department/Centre:	Others
Date Deposited:	01 Mar 2024 08:57
Last Modified:	01 Mar 2024 08:57
URI:	https://eprints.iisc.ac.in/id/eprint/83938

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