Trinodal Self-Penetrating Nets from Reactions of 1,4-Bis(alkoxy)-2,5-bis(3,2’:6’,3’’-terpyridin-4’-yl)benzene Ligands with Cobalt(II) Thiocyanate

Abstract

The tetratopic ligands 1,4-bis(2-ethylbutoxy)-2,5-bis(3,2’:6’,3’’-terpyridin-4’-yl)benzene (1) and 1,4-bis(3-methylbutoxy)-2,5-bis(3,2’:6’,3’’-terpyridin-4’-yl)benzene (2) have been prepared and characterized by 1H and 13C{1H} NMR, IR, and absorption spectroscopies and mass spectrometry. Reactions of 1 and 2 with cobalt(II) thiocyanate under conditions of crystal growth at room temperature result in the formation of [{Co(1)(NCS)2}·MeOH·3CHCl3]n and [{Co(2)(NCS)2}·0.8MeOH·1.8CHCl3]n. Single-crystal X-ray diffraction reveals that each crystal lattice consists of a trinodal self-penetrating (62.84)(64.82)(65.8)2 net. The nodes are defined by two independent cobalt centres and the centroids of two crystallographically independent ligands which are topologically equivalent.

Stars and stripes: hexatopic tris(3,2′:6′,3′′-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers

“…20,28 However, the coordination behaviour of bis(3,2′:6′,3″-tpy) ligands remains little explored. [29][30][31] In the present work, we extend our investigations of tetratopic bis(3,2′:6′,3″-tpy) and bis(4,2′:6′,4″-tpy) to hexatopic tris(3,2′:6′,3″-tpy) and tris(4,2′:6′,4″-tpy) ligands.…”

A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)2 and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene Ligands

“…1.2 n C 6 H 4 Cl 2 , which assembled into a 3D (6 5 .8) cds net [ 20 ]. In contrast, use of CHCl 3 solutions of 10 and 11 ( Scheme 3 ) and a MeOH solution of Co(NCS) 2 produced trinodal self-interpenetrating (6 2 .8 4 )(6 4 .8 2 )(6 5 .8) 2 nets, with powder X-ray diffraction data confirming that the single crystal structures were representative of the bulk materials [ 21 ]. In each of these structures (CSD refcodes KOXJEP, NORVAU and NORVOI), the asymmetric unit contains either one or two, crystallographically independent half-ligands with the second half generated by inversion.…”

The terpyridine isomer game: from chelate to coordination network building block

“…All products have the same [Co(NCS) 2 (L) 2 ] n stoichiometry (ignoring solvent molecules) and adopt 3D-networks. 45,51,52 Fig. 8 compares the conformations of the coordinated ligands 8, 9 and 11; [Co(NCS) 2 (10) 2 ] n and [Co(NCS) 2 (9) 2 ] n crystallize in the C2/c space group with similar cell dimensions and the structures are similar.…”

“…8 compares the conformations of the coordinated ligands 8, 9 and 11; [Co(NCS) 2 (10) 2 ] n and [Co(NCS) 2 (9) 2 ] n crystallize in the C2/c space group with similar cell dimensions and the structures are similar. 52 Ligands 9, 10 and 11 adopt conformations in which (i) the 3,2 0 :6 0 ,3 00 -tpy domains are close to coplanar and (ii) each 3,2 0 :6 0 ,3 00 -tpy adopts conformation II defined in Scheme 3. In contrast, coordinated 8 adopts a conformation in which (i) the 3,2 0 :6 0 ,3 00 -tpy domains are approximately orthogonal and (ii) each 3,2 0 :6 0 ,3 00 -tpy adopts conformation I in Scheme 3.…”

“…9 illustrates the self-penetrating network. 52 The reproducibility of the assembly with ligands 9 and 10 is important, and investigations with related tetratopic ligands are continuing.…”