Coordination Polymers from Calixarene-Like [Cu₂(Dicarboxylate)₂]₄ Building Blocks:  Structural Diversity via Atropisomerism

Abstract

The self-assembly of [Cu2(dicarboxylate)2]4 nanoscale secondary building units (nSBUs) into coordination polymers can occur in such a way that a range of calix-like atropisomers can exist. Eight compounds have been prepared and crystallographically characterized via reaction between Cu(NO3)2 and angular dicarboxylate ligands: {[Cu2(bdc)2(py)2]4•guest} n (1a), {[Cu2(bdc)2(py)2]4•4nitrobenzene•2EtOH} n (1b), {[Cu2(bdc)2(4-pic)2]4•4o-dichlorobenzene} n (2), {[Cu2(5-OEt-bdc)2(py)2]4•8H2O} n (3), {[Cu2(5-OPr-bdc)2(py)2]4•guest } n (4), {[Cu2(pdc)2(py)2]4•4MeOH} n (5), {[Cu2(pdc)2(4-pic)2]4•4H2O} n (6), and {[Cu2(tdc)2(MeOH)2]4•4naphthalene•8MeOH} n (7). The following atropisomers, all of which have also been observed in calixarenes, were observed: (a) cone (1a, 3, and 4); (b) partial cone (1b); (c) 1,2-alternate (2 and 5−7); and (d) 1,3-alternate (1a, 3, and 4). The similarities and differences between the crystal structures of 1−7 are detailed herein.

Crystal structure of catena-poly[diaqua-(μ2-5-methylisophthalato-κ2 O:O′)(μ2-1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene-κ2 N:N′)], NiC21H22O6N6

“…Ni1 is six-coordinated with a distorted octahedral environment by two carboxylic O atoms from two mip ligands, two N atoms from two bitb ligands and two coordinated water molecules. The bond angles around Ni1 range from 85.36(5) to 180.0°, the Ni1-O bond lengths vary from 2.0910(13) to 2.1103(12) Å, and the Ni1-N bond distances are 2.0852 (16). The mip ligand is completely deprotonated.…”

“…The results show that different substituents lead to different structures and properties. However, the study of CPs based on 5-methylisophthalate has been reported rarely [16,17]. In order to study the effect of a single methyl group on structural topologies and physicochemical properties we chose 5-methylisophthalic acid along with 1,4-bis(triazol-1-ylmethyl) benzene to elaborate new complexes.…”

Construction of Functionalized Metallosupramolecular Tetragonal Prisms via Multicomponent Coordination-Driven Self-Assembly

“…Ligands 3d 16 and 3f 17 were prepared according to reported procedures. Deuterated solvents were purchased from Cambridge Isotope Laboratory (Andover, MA).…”

Síntesis de 2,8,14,20-tetra-n-butilpirogalol[4]areno y estudio computacional conformacional

“…Igualmente, la metodología de síntesis y el control de las variables conformacionales de estas moléculas han mejorado considerablemente en los últi-mos años [15,16,17]. Recientemente, estos macrociclos han recibido una mayor atención por sus potenciales usos como: (i) plataformas moleculares para intercambio de ligandos con metales [18], (ii) materiales poliméricos [19,20,21], (iii) sistemas de auto-ensamblaje [22,23,24,25,26,27,28,16], (iv) centros de reacción de procesos catalíticos [29,30,31]; al igual que para la extracción de metales pesados [32,33,34,35], la detección de iones [36,37,38,39,40]; y especialmente como cápsulas moleculares para el transporte de compuestos específicos [41,42,43], filtros moleculares en estado sólido [34,44,45], y como modelos de membranas en solventes polares y estado cristalino [46,47].…”