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Water‐Soluble Derivatives of Octanuclear Iron–Oxido–Pyrazolato Complexes – an Experimental and Computational Study
Author(s) -
Das Soma,
Chakraborty Indranil,
Skachkov Dmitry,
Ahmadi Majid,
Ishikawa Yasuyuki,
Baran Peter,
Raptis Raphael G.
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200428
Subject(s) - chemistry , supramolecular chemistry , aqueous solution , electrospray ionization , crystallography , solvation , molecule , density functional theory , nuclear magnetic resonance spectroscopy , dynamic light scattering , mass spectrometry , computational chemistry , stereochemistry , crystal structure , organic chemistry , nanotechnology , nanoparticle , materials science , chromatography
Two water‐soluble iron–pyrazolato complexes (compounds 3 and 4 ), [Fe 8 ], have been prepared by introducing twelve hydroxyalkyl groups to the periphery of the approximately spherical octanuclear molecule. They are contrasted with their two organosoluble chloroalkyl analogues (compounds 1 and 2 ). All four complexes were characterized in solution by 1 H NMR and electrospray ionization mass spectrometry. The one‐electron‐reduction product of water‐soluble 3 , [Fe 8 ] – , was structurally characterized by single‐crystal X‐ray diffraction analysis. In aqueous media, the four terminal Fe–Cl bonds of [Fe 8 ] are partially hydrolyzed, and the resulting chlorido–aqua–hydroxido species form supramolecular nanoscale aggregates, as determined by dynamic light scattering and electron microscopy. Preliminary computational studies with DFT methods were employed to model the H‐bonding interactions controlling the competing solvation and aggregation processes.