Issue 31, 2022

Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage

Abstract

A pyridine/aniline appended unsymmetrical bis-monodentate ligand N-(3-aminophenyl)nicotinamide, Lun is synthesized via condensation of nicotinic acid with excess m-phenylene diamine. A low-symmetry binuclear complex of the Pd2L′2Lun2 type and an extremely rare trinuclear complex of the Pd3Lun6 type are produced by self-assembly of the ligand Lun with cis-protected palladium(II) (i.e., PdL′) and palladium(II), respectively. Two isomers (i.e. [(2,0), (2,0)] and [(1,1), (1,1)]-forms) are theoretically possible for the Pd2L′2Lun2-type complex whereas nine isomers can be envisaged in the case of the Pd3Lun6-type arrangement. However, one of the isomers of the Pd2L′2Lun2-type complex as well as the one for the Pd3Lun6-type complex are experimentally obtained. The exclusive formation of specific isomers could be predicted from the 1D/2D NMR study in the solution state and the DFT calculations in the gas phase/implicit solvent media. The formation of the predicted all-(1,1)-[Pd2(en)2Lun2](NO3)4 has been confirmed by a single-crystal XRD study. DFT calculations for the isomers of the Pd3Lun6-type arrangement show that a [cis(2,2), cis(2,2), cis(2,2)] isomer is energetically favourable than the alternatively predicted [trans(2,2), trans(2,2), trans(2,2)] isomer. Conformational changes within the build of the exclusively formed isomers are proposed on the basis of NMR study.

Graphical abstract: Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage

Supplementary files

Article information

Article type
Paper
Submitted
19 ሜይ 2022
Accepted
28 ጁን 2022
First published
28 ጁን 2022

Dalton Trans., 2022,51, 11650-11657

Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage

S. S. Mishra and D. K. Chand, Dalton Trans., 2022, 51, 11650 DOI: 10.1039/D2DT01571D

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