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Differing Patterns in the Self-Assembly of Radially Anchored Imidazoles, 1,3,5-Tris(1H-imidazol-2-yl)benzene and 1,3-Bis(1H-imidazol-2-yl)benzene

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Abstract

The novel 3-fold symmetric 1,3,5-tris(1H-imidazol-2-yl)benzene, having a propensity for a 3-fold salt formation by hydrogen bonding at the periphery, was prepared from oxidation of the hexahydro imidazole precursor. The transformation proved difficult and, of the many reagents tried, only barium manganate and o-iodoxy benzoic acid were successful. The oxidation to the aromatic 1,3,5-tris imidazolyl benzene produces dramatic changes, particularly when the X-ray structures of their tris-TFA (trifluoroacetic acid) salts are compared. While the hexahydro precursor exhibited a herringbone type arrangement in the crystal, the oxidation resulted in almost co-planar molecules that formed parallel stacks separated by 3.57 Å between the atoms in separate planes. 1,3-Bis(1H-imidazole-2-yl)benzene is an attractive core unit for assembly using a variety of auxiliaries. Several attempts to complex the bis-imidazole with organic acids failed. These efforts lead to the serendipitous discovery of a novel tetrameric assembly, mediated by water molecules, which was confirmed by crystallization of the bis imidazole from water.

Index Abstract

Differing Patterns in the Self-Assembly of Radially Anchored Imidazoles, 1,3,5-Tris(1 H -imidazol-2-yl)benzene and 1,3-Bis(1 H -imidazol-2-yl)benzene

A. Infinite stacks of the TFA salt from 1,3,5-tris(1H-imidazol-2-yl)benzene with a separation of 3.57 Å between atoms in separate planes (The TFA moiety has been omitted for clarity).

B. Tetrameric assembly of 1,3-bis(1H-imidazol-2-yl)benzene, mediated by water molecules.

Differing Patterns in the Self-Assembly of Radially Anchored Imidazoles, 1,3,5-Tris(1 H -imidazol-2-yl)benzene and 1,3-Bis(1 H -imidazol-2-yl)benzene

Y.B.R.D. Rajesh, (2) Subramania Ranganathan, (2)* Richard D. Gilardi (1,3) and Isabella L. Karle, (1)*

(1) Laboratory for the Structure of Matter, Naval Research Laboratory, Washington, D.C. 20375-5341

(2) Discovery Laboratory, Organic III, Indian Institute of Chemical Technology, Hyderabad 500 007, India

(3) Retired

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Acknowledgement

SR and Rajesh are grateful to Department of Biotechnology, New Delhi for financial assistance. Work performed at the Naval Resesearch Laboratory was supported by the Office of Naval Research.

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Authors and Affiliations

  1. Discovery Laboratory, Organic III, Indian Institute of Chemical Technology, Hyderabad, 500 007, India

    Y. B. R. D. Rajesh & Subramania Ranganathan

  2. Laboratory for the Structure of Matter, Naval Research Laboratory, 4555 Overlook Avenue, S.W, Washington, DC, 20375-5341, USA

    Richard D. Gilardi & Isabella L. Karle

Authors
  1. Y. B. R. D. Rajesh
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  2. Subramania Ranganathan
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  3. Richard D. Gilardi
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  4. Isabella L. Karle
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Correspondence to Isabella L. Karle.

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Richard D. Gilardi—Retired.

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Rajesh, Y.B.R.D., Ranganathan, S., Gilardi, R.D. et al. Differing Patterns in the Self-Assembly of Radially Anchored Imidazoles, 1,3,5-Tris(1H-imidazol-2-yl)benzene and 1,3-Bis(1H-imidazol-2-yl)benzene. J Chem Crystallogr 38, 39–48 (2008). https://doi.org/10.1007/s10870-007-9286-6

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