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Article

Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers

Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland
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Received: 11 December 2020 / Revised: 20 January 2021 / Accepted: 26 January 2021 / Published: 2 February 2021
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 = 15 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. View Full-Text
Keywords: 3,2′:6′,3″-terpyridine; coordination polymer; copper(II) acetate; paddle-wheel building block; X-ray diffraction 3,2′:6′,3″-terpyridine; coordination polymer; copper(II) acetate; paddle-wheel building block; X-ray diffraction
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MDPI and ACS Style

Rocco, D.; Novak, S.; Prescimone, A.; Constable, E.C.; Housecroft, C.E. Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers. Chemistry 2021, 3, 182-198. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3010015

AMA Style

Rocco D, Novak S, Prescimone A, Constable EC, Housecroft CE. Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers. Chemistry. 2021; 3(1):182-198. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3010015

Chicago/Turabian Style

Rocco, Dalila, Samantha Novak, Alessandro Prescimone, Edwin C. Constable, and Catherine E. Housecroft 2021. "Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers" Chemistry 3, no. 1: 182-198. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3010015

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