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Issue 25, 2014
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Self-assembly of a family of suprametallomacrocycles: revisiting an o-carborane bisterpyridyl building block

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Abstract

The self-assembly of the o-carborane-based, bisterpyridyl monomer, 1,2-bis[4′-(4-ethynylphenyl)-2,2′:6′,2′′-terpyridine]-o-carborane, utilizing either ZnII or FeII in a precise metal : ligand ratio (1 : 1), generated a family of metallomacrocycles that were studied via ESI-TWIM-MS, 1H NMR, and 2D NMR (COSY, NOESY). Under kinetic control, via formation of FeII complexes, the main cyclic product was triangular, as is typical of 60°-based bisligands. Under thermodynamic control using more labile transition metal complexes, e.g. ZnII, the ratio of cyclic species was found to be concentration and temperature dependent, and under an adequate entropic driving force, the cyclic dimer was formed. This system was probed via variable temperature NMR to reveal dynamic equilibrium between the entropically favored dimer and enthalpically favored trimer.

Graphical abstract: Self-assembly of a family of suprametallomacrocycles: revisiting an o-carborane bisterpyridyl building block

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Article information


Submitted
03 Apr 2014
Accepted
02 May 2014
First published
06 May 2014

Dalton Trans., 2014,43, 9604-9611
Article type
Paper
Author version available

Self-assembly of a family of suprametallomacrocycles: revisiting an o-carborane bisterpyridyl building block

J. M. Ludlow III, M. Tominaga, Y. Chujo, A. Schultz, X. Lu, T. Xie, K. Guo, C. N. Moorefield, C. Wesdemiotis and G. R. Newkome, Dalton Trans., 2014, 43, 9604
DOI: 10.1039/C4DT00989D

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