pH Dependent Formation of Unprecedented Water–Bromide
Cluster in the Bromide Salts of PTP Assisted by Anion−π
Interactions: Synthesis,
Structure, and DFT Study
posted on 2014-02-05, 00:00authored byPrankrishna Manna, Saikat
Kumar Seth, Antonio Bauzá, Monojit Mitra, Somnath Ray Choudhury, Antonio Frontera, Subrata Mukhopadhyay
Two
new terpyridine derivatives [PTPH3](Br)3·3H2O (1) and [PTPH3](Br3)(Br)2·H2O (2), (PTP
= 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine)
were synthesized and characterized by single crystal X-ray diffraction
analyses. In 1, intricate combination of anion···π/π–π/π···anion
interactions generates the supramolecular network while 2 exhibits a combination of two different anion···π/π–π/π···anion
and anion···π···anion assemblies.
As anticipated, both of them are interlinked through hydrogen bonds
affording molecular networks, but surprisingly, 1 shows
hydrate aggregation and interactions with anions to generate water–bromide
cluster blends in the solid lattices. A search of the crystal structure
database (CSD) yielded only eight hits presenting an infinite tape
in the solid state structure formed by bromide anions and water molecules,
none of which had similar distribution of bromide and water as observed
in 1. Interestingly, in compound 1, the
bromide anion is involved in the formation of anion–water cluster
and also engaged in anion···π interactions, thus
generating a unique cluster of water–anion/anion···π/π–π/π···anion/anion–water
cluster network. The different networks have been investigated by
means of DFT calculations and the interactions characterized using
the Bader’s theory of “atoms-in-molecules”.