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Rational Design of Organically Functionalized Polyoxopalladates and Their Supramolecular Properties
Author(s) -
Yang Peng,
Li Hui,
Ma Tian,
Haso Fadi,
Liu Tianbo,
Fan Linyuan,
Lin Zhengguo,
Hu Changwen,
Kortz Ulrich
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705303
Subject(s) - supramolecular chemistry , hydrogen bond , amphiphile , chemistry , alkyl , crystallography , solvent , self assembly , fourier transform infrared spectroscopy , stereochemistry , crystal structure , polymer chemistry , molecule , copolymer , chemical engineering , organic chemistry , engineering , polymer
The Sr II ‐centered 12‐palladate(II) open‐cube {SrPd 12 (OAc) 3 } has been systematically evolved by substitution of the three acetate ligands by a library of saturated carboxylic acids with increasing chain lengths leading to four novel polyoxopalladates(II) with the formula [SrPd 12 O 6 (OH) 3 (PhAsO 3 ) 6 (L) 3 ] 4− (SrPd 12 L 3 , L=C n H 2 n +1 COO, n= 2 to 5). These first examples of surfactant‐type polyoxopalladates with a hydrophilic metal‐oxo unit and three hydrophobic alkyl chains were characterized in the solid state (single‐crystal XRD, FTIR, TGA), in solution ( 1 H, 13 C NMR spectroscopy), and in the gas phase (ESI‐MS). The two polyanions SrPd 12 L 3 with chain lengths of 5 and 6 are the first examples of polyoxopalladates that are soluble and stable in organic media. The Na salts of the amphiphilic polyoxopalladates SrPd 12 L 3 were shown to self‐assemble into “blackberry”‐type spherical supramolecular structures in dilute solutions, of which an unusual “volcano”‐shaped trend of assembly size versus solvent polarity is chiefly influenced by directional hydrogen bonding interactions.