Dan Dumitrescu

New "pyrene box" cages for adaptive guest conformations.

The possibility of controlling the compression extent and the coiling shape of the 1,12-diammoniumdodecane guest is shown by changing the dimensions of the internal space of the host guanidinium 1,3,5,8 pyrene-tetrasulfonate PTS(4-) crystalline capsules by using guanidinium (G(+)), amino-guanidinium (AG(+)), and diaminoguanidinium (A2G(+)) cations.

Reply to A Computational Evaluation of the Evidence for the Synthesis of 1,3-Dimethylcyclobutadiene in Solid State and Aqueous Solution—Beyond the Experimental Reality

Following earlier reports on the photochemical synthesis of 1,3-dimethylcyclobutadiene in a protective host matrix, theoretical calculations for the formation of that adduct have been recently performed by Rzepa. The author formulated criticisms based mainly on density functional theory calculations of (1)H NMR spectra. According to Rzepa the calculated spectra do not correspond with our measured spectra, which leads him to the conclusion that our interpretation is wrong, and that mainly cyclobutadiene has not been stabilized or even synthesized; we believe, however, that the initial model that Rzepa used for his calculations does not correspond to chemical reality or is at the very least a crude simplification of it, which implies that his calculations cannot match, in every point, our experimental spectra. Rzepas simplified models might be reasonable from the theoretical point of view; however, in the case of assessment in the solid state, the theoretical setup does not force the system to preserve the confined stabilizing space defined by the crystalline matrix for encapsulated hosts in the solid state. Inversely, in the case of solution modeling, the theoretical setup is too rigid to properly assess the complex equilibria occurring in solution and to accurately determine the NMR spectra of exchanging species in solution. The inconsistency between our experimental results and the results of the theoretical models proposed by Rzepa is such that his conclusions are considered to be too far from experimental reality. Accurate modeling taking in account reasonable experimental details would be a worthwhile endeavor.

Crystallisation-Driven Self-Sorting of H-Bonded Guanidinium or Sodium Sulfonate Constitutional Molecular Frameworks

Four single crystal structures were obtained in order to better understand the difference between the crystallisation-driven formation of solid state organo-sulfonate guanidinium superstructures and their sodium salt analogues. 5-Formyl-2-furfuryl sulfonate and 4,4′-diamino-2,2′-biphenyl disulfonate were chosen as anions due to functional and geometrical considerations together with guanidinium, aminoguanidinium, and sodium cations. 5-Formyl-2-fufuryl sulfonate reacts with aminoguanidinium cation in water leading to an imino-zwitterionic compound, able to form on its own a guanidinium-sulfonate superstructure in crystalline state.

A Constrained Disorder Refinement: “Reinvestigation of “Single‐Crystal X‐ray Structure of 1,3‐Dimethylcyclobutadiene” by M. Shatruk and I. V. Alabugin”

Shatruk and Alabugin propose an alternative structural model for the observed electron density that we have attributed to the photochemical formation of 1,3-dimethylcyclobutadiene in a protective solid crystalline matrix. The main criticism from Shatruk and Alabugin concerns the modeling of the disorder in the calixarene cavity and in particular the neglect of a residual electron density close to the O1 atom. We published (Chem. Eur. J. 2011, 17, 10021) our opinion concerning this ignored peak in the Supporting Information of the paper. The current response to the Correspondence demonstrates that Shatruk and Alabugin have over-modeled our data by assigning a small electron density peak, which is hardly more than the density corresponding to a hydrogen atom, to an under-occupied oxygen site, using inappropriate refinement contraints.