Self-Assembly of a Pd8Macrocycle and Pd12Homochiral Tetrahedral Cages Using Poly(tetrazolate) Linkers

Howlader, P and Bhandari, P and Chakraborty, D and Clegg, JK and Mukherjee, PS (2020) Self-Assembly of a Pd8Macrocycle and Pd12Homochiral Tetrahedral Cages Using Poly(tetrazolate) Linkers. In: Inorganic Chemistry, 59 (20). pp. 15454-15459.

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Abstract

A two-dimensional molecular square (MC) was obtained by the self-assembly of a bis(tetrazole) linker, 4,4′-bis(1H-tetrazol-5-yl)-1,1′-biphenyl (H2L1), with a square-planar metal acceptor M [M = (tmeda)Pd(NO3)2, where tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine] in dimethyl sulfoxide (DMSO) followed by crystallization. The uncommon 2,3-binding mode through N atoms of the tetrazole rings in this assembly leads to the formation of an octanuclear molecular square. The molecular square MC [Pd8(L1)4(NO3)8] is unstable in DMSO and slowly converts to a dynamic mixture of a 3D tetrahedral cage T1 [Pd12(L1)6(NO3)12] and the macrocycle MC. A tetrahedral cage (T1) is formed by the usual 1,3-binding mode of the tetrazole rings. However, self-assembly of the T1 [Pd12(L1)6(PF6)12] was possible to access in the pure form in a less polar solvent like acetonitrile. The pure T1 [Pd12(L1)6(PF6)12] also converts to a mixture of T1 and MC in DMSO. Interestingly, when a tris(tetrazole) linker, tris(4-(1H-tetrazol-5-yl)phenyl)amine (H3L2), was treated with the acceptor M, it produced a tetrahedral nanocage T2 [Pd12(L2)4(NO3)12] through 1,3-binding mode of the tetrazole rings without any trace of an octahedral cage through 2,3-binding mode of the tetrazole moieties.

Item Type:	Journal Article
Publication:	Inorganic Chemistry
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Mixtures; Organic solvents; Self assembly, Dimethyl sulfoxide (DMSO); Macrocycles; Molecular squares; Nanocages; Polar solvents; Square-planar metals; Tetrazoles, Dimethyl sulfoxide
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	11 Feb 2023 03:06
Last Modified:	11 Feb 2023 03:06
URI:	https://eprints.iisc.ac.in/id/eprint/80179

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