Abstract
We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (1), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (2), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (3), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (4), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (5), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu2(μ-OAc)4L]n 1D-coordination polymers with L = 1–5 have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in 1 by an F substituent in 2 has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for 1 or H...F for 2) are only secondary packing interactions. Upon going from [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n to [Cu2(μ-OAc)4(3)]n, [Cu2(μ-OAc)4(4)]n, and [Cu2(μ-OAc)4(5)]n·nMeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility.
Highlights
For many chemists, the word “terpyridine” is synonymous with 2,20 :60,200 -terpyridine, the coordination chemistry and applications of which are exceptionally well developed [1,2,3,4,5]
Chemistry 2021, 3, Abstract: We report the preparation and characterization of 40 -([1,10 -biphenyl]-4-yl)-3,20 :60,300 -terpyridine
From the perspective of assembling coordination polymers and networks, the bis-chelating nature of tpy tends to restrict its use to {M(tpy)2 } units bearing peripheral functionalities that can act as metal-binding domains or polytopic ligands containing multiple tpy metal-binding domains
Summary
The word “terpyridine” is synonymous with 2,20 :60 ,200 -terpyridine (tpy), the coordination chemistry and applications of which are exceptionally well developed [1,2,3,4,5]. From the perspective of assembling coordination polymers and networks, the bis-chelating nature of tpy tends to restrict its use to {M(tpy)2 } units bearing peripheral functionalities that can act as metal-binding domains or polytopic ligands containing multiple tpy metal-binding domains. Such “expanded ligands” with the {M(tpy)2 } unit on the “inside” of the metalloligand have gained significant attention [6]. While retaining a terpyridine building block, the most efficient way to access 1Dcoordination polymers and 2D- and 3D-coordination networks is to turn to other isomers of terpyridine [8]. The coordination chemistry of 4,20 :60 ,400 -terpyridines (4,20 :60 ,400 -tpy (I), Scheme 1)
Sign-in/Register to view highlights & summary 
Published Version (
Free)
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call