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Pyridyl terpyridine; metalloligands; halo functionalization; X-ray structures; spacer ligands

A new series of zinc phosphate based novel elongated ditopic N,N^Ꞌ-metalloligands [Zn(Xdipp)(pyterpy)]₂.2MeOH (X= H (1), Cl (2), Br (3), I (4)], exemplifying expanded 4,4^Ꞌ-bipyridine spacer family, has been prepared by reacting 4^Ꞌ-(4^ꞋꞋ-pyridyl)-2,2^Ꞌ:6^Ꞌ,2^ꞋꞋ-terpyridine (pyterpy), 2,6-iisopropylphenylphosphate (dippH2) or its para-halo functionalized derivatives X-dippH₂ (X = Cl, Br, I) with Zn(OAc)₂.2H₂O in a mixture of solvents at room temperature. The formation of these metalloligands has been confirmed by their spectroscopic and analytical data. Solution and solid-state stability of these complexes have beenconfirmed by both mass spectroscopy and thermogravimetric analysis. The solid-state structures of 1–4 have further been established by single crystal X-ray diffraction studies, revealing that the N,N^Ꞌ-distance in these systems can be expanded approximately to 23 A^° , as against the 7 A^° separation observed for 4,4^Ꞌ-bipyridine.Compounds 2–4, which contain two pyridyl nitrogen centers and two C–X functionalities that are orthogonal to each other, could offer new possibilities in their use as metalloligand to build extended 2-D and 3-D solids

GULZAR A BHAT RAMASWAMY MURUGAVEL¹

1. Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400 076, India

Published

8 September 2020

Manuscript received

20 April 2020

Manuscript revised

23 May 2020

Accepted

5 June 2020