Correction to “Pyridine Ligand Rotation in Self-Assembled Trigonal Prisms. Evidence for Intracage Solvent Vapor Bubbles”

Challenges in the Structure Determination of Self-Assembled Metallacages: What Do Cage Cavities Contain, Internal Vapor Bubbles or Solvent and/or Counterions?

“…Such reclosure to 3­( n ) would presumably be identical with the last step of the original synthesis of 3­( n ) by self-assembly. Even though the computations later turned out to be incorrect due to programming and input errors, they played a heuristic role by hinting at a possible explanation of the odd observed Eyring parameters. The value Δ S ⧧ = ∼60 cal·mol –1 ·K –1 roughly agreed with expectations for the excluded volume entropy of a spherical bubble with a volume equal to that estimated for the internal cavity in 3­(3) , and encouraged us to propose that at equilibrium a solvent vapor bubble is present. , …”

“…46−49 The results of a set of molecular dynamics calculations published by our group 29 that predicted bubble formation in a molecular tube unfortunately are wrong due to computer programming errors in the version of the TINK program 50 that was originally used, and could not be reproduced. 51 So far, to our knowledge there exists no definitive experimental proof for the presence or absence of solvent vapor bubbles in the numerous self-assembled cage molecules that have been synthesized and examined in solution. The experimental data reported in our previous paper 29 provided rather indirect evidence that suggested but certainly did not prove that a bubble might be present in the nitromethane solution of a dodecacation produced by the self-assembly of three tetrapodal connectors 1 with six linkers 2.…”

“…The work was primarily focused on water, − but other solvents could behave similarly . The structure of a liquid–vapor interface in the presence of a hard wall in the transition region was studied decades ago. , Molecular dynamics simulations of two paraffin plates immersed in water and located closer than a critical distance apart revealed a spontaneous drying transition, i.e., a cavity-induced liquid–gas phase transition. , The effect of hydrophobic surface morphology and free energy barriers on the dynamics of capillary evaporation has also been examined. − The results of a set of molecular dynamics calculations published by our group that predicted bubble formation in a molecular tube unfortunately are wrong due to computer programming errors in the version of the TINK program that was originally used, and could not be reproduced …”