Issue 24, 2021

Post-synthetic modification of supramolecular assemblies of β-diketonato Cu(ii) complexes: comparing and contrasting the molecular topology by crystal structure and quantum computational studies

Abstract

The post-synthetic approach is a powerful strategy to modify organic linkers and/or metal node functionality without disrupting the parent metal and ligand coordination. Engineering new crystal forms of the same molecule and investigating the relationship among them is a challenging area of crystallography to explore the structure–property relationship. In this regard, a new crystal form of homoleptic 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (TFNB) Cu(II) complex [Cu(TFNB)2(C2H6SO)] (1) is characterized by the single crystal X-ray diffraction method which revealed that complex 1 is an isostructural solvate of previously reported [Cu(TFNB)2(C2H6SO)2] (2). In complex 1, a single DMSO solvent molecule is apically coordinated to the Cu(II) ion to form a distorted square pyramidal geometry with two chelating rings of TFNB, while in complex 2, the solvent molecules are present in pairs related by the inversion center leading to a six coordinated octahedral geometry. Besides, the newly synthesized heteroleptic Cu(II) complex of TFNB with 8-hydroxyquinoline exists in two pseudopolymorphic forms, [Cu(TFNB)(8HQ)]2 (3) and [Cu(TFNB)(8HQ)]·CH3COOH (4) via non-bridging solvent incorporation. Complex 3 is a phenoxide bridged binuclear complex that adopts a distorted square pyramidal geometry. In complex 4, the bridging action of phenoxide is broken by the effect of a guest solvent (acetic acid) molecule, leading to the formation of a discrete mononuclear complex with a square planar geometry. The solvent induced structural transformations on the metal coordination sphere and molecular interaction topology of Cu(II) complexes, via single crystal coordinated solvent exchange (complexes 1 and 2) and solvent molecule participation in the crystal lattice (complexes 3 and 4), were comparatively analyzed and investigated by combined crystallographic and quantum computational studies.

Graphical abstract: Post-synthetic modification of supramolecular assemblies of β-diketonato Cu(ii) complexes: comparing and contrasting the molecular topology by crystal structure and quantum computational studies

Supplementary files

Article information

Article type
Paper
Submitted
03 Mar 2021
Accepted
12 May 2021
First published
03 Jun 2021

CrystEngComm, 2021,23, 4344-4369

Post-synthetic modification of supramolecular assemblies of β-diketonato Cu(II) complexes: comparing and contrasting the molecular topology by crystal structure and quantum computational studies

Mahesha, K. J. Pampa, C. S. Karthik, M. K. Hema, P. Mallu and N. K. Lokanath, CrystEngComm, 2021, 23, 4344 DOI: 10.1039/D1CE00304F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements