Guanidinium Alkynesulfonates with Single‐Layer Stacking Motif: Interlayer Hydrogen Bonding Between Sulfonate Anions Changes the Orientation of the Organosulfonate R Group from “Alternate Side” to “Same Side”

Abstract

Hydrolyses of HC[triple bond]CSO3SiMe3 (1) and CH3C[triple bond]CSO3SiMe3(2) lead to the formation of acetylenic sulfonic acids HC[triple bond]CSO3H.2.33H2O (3)and CH3C[triple bond]CSO3H.1.88H2O (4). These acids were reacted with guanidinium carbonate to yield [+C(NH2)3][HC[triple bond]CSO3] (5) and [+C(NH2)3][CH3C[triple bond]CSO3] (6). Compounds 1-6 were characterized by spectroscopic methods,and the X-ray crystal structures of the guanidinium salts were determined.The X-ray results of 5 show that the guanidinium cations and organosulfonate anions associate into 1D ribbons through R2(2)(8) dimer interactions,whereas association of these ions in 6 is achieved through R2(2)(8) and R1(2)(6) interactions. The ribbons in 5 associate into 2D sheets through R2(2)(8) dimer interactions and R3(6)(12) rings, whereas those in 6 are connected through R1(2)(6)and R2(2)(8) dimer interactions and R4(6)(14) rings. Compound 6 exhibits a single-layer stacking motif similar to that found in guanidinium alkane- and arenesulfonates, that is, the alkynyl groups alternate orientation from one ribbon to the next. The stacking motif in 5 is also single-layer, but due to interlayer hydrogen bonding between sulfonate anions, the alkynyl groups of each sheet all point to the same side of the sheet.

Toward Understanding the Origin of Structural Phase Transition in Guanidinium Pyridinium 1,5-Naphthalenedisulfonate

“…Ward and co-workers performed a systematic investigation of the family of guanidinium organo(di)sulfonate compounds. − The attracting features of these compounds include (i) two-dimensional H-bonding networks, (ii) adjustable porosity, and (iii) ordered arrays of guest molecules. Modifications of the G and S components significantly alter the crystal packings of the corresponding guanidinium organo(di)sulfonate compounds. − …”

Rolling Up the Sheet: Constructing Metal–Organic Lamellae and Nanotubes from a [{Mn3(propanediolato)2}(dicyanamide)2]n Honeycomb Skeleton

“…The discovery of carbon nanotubes (CNTs), especially single-walled carbon nanotubes (SWNTs), in conjunction with their outstanding physical and chemical properties, has stimulated extensive investigation into nanotubes of other compositions, such as metal oxides, metal chalcogenides, and organic compounds . In general, the formation of these tubular structures can be regarded as the rolling-up conversion of their corresponding layered materials.…”

Guanidinium vs. Ammonium Surfactants in Soft‐Templating Approaches: Nanostructured Silica and Zwitterionic i‐Silica from Complementary Precursor–Surfactant Ion Pairs

“…For this reason, we particularly envisioned the use of guanidinium‐type surfactants since guanidinium cations show high affinities towards sulfonate anions. The complementarity of guanidinium and sulfonate ions gave rise to a large variety of self‐assembled molecular crystals starting from organodisulfonates and guanidinium counterions 44–46. For this reason, we decided to study the hydrolysis/polycondensation behaviour of the ammonium sulfonate precursor 2 in the presence of guanidinium‐type surfactants and to compare these materials with the previously reported materials, obtained in the presence of CTAB.…”