Salt Cluster Attachment to Crown Ether Decorated Phthalocyanines in the Gas Phase

Abstract

Crown ether decorated phthalocyanines were designed to form rigidly eclipsed aggregates with metal ions being sandwiched between the molecules. We studied tetra-[18]crown-6 ether functionalized zinc phthalocyanine (ZnPcTetCr) in the presence of excess NaCl by electrospray ionization mass spectrometry. ZnPcTetCr was found to form aggregates in the gas phase to which several neutral NaCl molecules are attached. Collision-induced dissociation experiments revealed that the ions observed in the positive- and negative-ion modes possess remarkably different structures. Their fragmentation behavior indicates that the sodium ions providing the charge of the positively charged aggregates are strongly bound inside the crown ether moieties, while the neutral salt units are less strongly attached. However, in the negatively charged ions, none of the sodium ions is embedded in the crown ether moieties, and the NaCl molecules were found to be attached as one large, weakly bound cluster.

Photodissociation of Sodium Iodide Clusters Doped with Small Hydrocarbons

“…Particularly well studied is the adsorption of ammonia and water to a variety of alkali halide species. Drewello and co‐workers studied the stability of salt clusters attached to crown ether decorated phthalocyanines . Sodium iodide clusters were subject of several gas phase studies.…”

“…Drewello and co-workers studied the stability of salt clusters attached to crown ether decorated phthalocyanines. [26] Sodium iodide clusters were subject of several gas phase studies. Ouyang et al investigated the collision cross sectionw ith mobility measurements [27] and Blades et al studied the hydration energyo fN a 2 I + .…”

Recent advances in mass spectrometry studies of non-covalent complexes of macrocycles - A review

“…A clear example of the study of the existence of functionalized crown ether aggregates in gas phase was published by Drewello et al [121,122]. Their research was focus on the aggregation behavior of the tetra- [18]crown-6 ether functionalized zinc-pthalocianine (ZnPcTetCr) in absence of coordinating metal cation using ESI-MS.…”

Unexpected Supramolecular Induced Redox Switching in Sandwich Gd Bisphthalocyaninate

“…The introduction of substituents responsible for supramolecular assembly opens up new opportunities to organize phthalocyanine molecules in a specific way 3,[30][31][32][33][34][35][36] . One of the brightest examples of such substituents are crown ethers [37][38][39][40][41][42][43][44] , which enable the cationinduced assembly of sandwich lanthanide complexes, leading to control of their functional properties [45][46][47][48][49][50][51][52][53][54][55] . Alkali cations with an ionic radius larger than the crown ether cavity can connect two adjacent molecules forming dimers 41,[55][56][57][58][59][60][61] or longer oligomers [62][63][64][65] (Fig.…”