Tuning the coordination chemistry of cyclotriveratrylene ligand pairs through alkyl chain aggregation

Abstract

Propylated cyclotriveratrylene (CTV) ligands display different coordination chemistry over their methylated congeners as a result of increased solubility, an affinity for alkyl chain aggregation and steric factors.

Controlling the assembly of cyclotriveratrylene-derived coordination cages

“…Whilst this is testament to their hosting ability, it demonstrates just how easily their self-assembly can be perturbed and how challenging their self-assembly can be to predict. Similar offset M 2 L 2 assemblies of derivatised CTVs have been observed in both coordination 34 and organometallic 35 complexes, alongside purely covalent species. 36…”

“…Whilst this is testament to their hosting ability, it demonstrates just how easily their self-assembly can be perturbed and how challenging their self-assembly can be to predict. Similar offset M 2 L 2 assemblies of derivatised CTVs have been observed in both coordination 34 and organometallic 35 complexes, alongside purely covalent species. 36 The second noteworthy complex of M 2 L 2 stoichiometry is the dimeric [Ag 2 (2) 2 (MeCN) 2 ] 2+ capsule (where 2 = (AE)-tris-(3-pyridylmethylamino)cyclotriguaiacylene), which is formed from the self-assembly of ligand 2 and silver(I) hexafluorophosphate (PF 6 À ) in acetonitrile (MeCN) solvent, Fig.…”

Studies of Multicenter and Intermolecular Dihydrogen B–H···H–C Bonding in [4,8,8′‐exo‐{PPh3Cu}‐4,8,8′‐(μ‐H)3‐commo‐3,3′‐Co(1,2‐C2B9H9)(1′,2′‐C2B9H10)]

“…Thus, in [Ag(glu)(Cobdc)] {glu = glutaronitrile, NC(CH 2 ) 3 CN} [40] only atoms of the upper belt of the {nido-C 2 B 9 H 11 } ligands most distant from the cage carbon atoms, due to their most hydridic character, are involved in the B-H···Ag bonding interaction. [Ag(C 6 H 6 )-(MeC 6 H 4 Me)(Cobdc)], [41] [Ag(MeC 6 H 4 Me)(Cobdc)], [41] [Ag(adi)(Cobdc)], [40] [Ag(pim)(Cobdc)][Ag(Cobdc)], [42] [Ag 3 (sub) 2 (Cobdc) 3 ], [42] and [Ag(L1p)(Cobdc)] [43] [23] This, in fact, indicates the predominantly electrostatic nature of M···Cobdc bonding. The same was concluded from the 1 H and 11 B NMR spectra of 1, which manifest stereochemical non-rigidity caused by the fast moving of the Cu-containing group between the B8, B4Ј, and B8Ј atoms of the carborane cage ligands.…”

Coordination polymers with embedded recognition sites: lessons from cyclotriveratrylene-type ligands

“…Pillararenes, crown ethers, cucurbiturils and cyclodextrins have also been employed. Our own work, [9][10][11][12][13][14][15][16][17][18][19][20][21] alongside that of other research groups, [22][23][24][25][26] has investigated the use of functionalised cyclotriveratrylenes (CTVs) as bridging ligands for coordination polymers. Cyclotriveratrylene (CTV) is a bowl-shaped molecular host with a tribenzo [a,d,g] cyclononatriene core.…”