Complex Immobilization via Spacers

Styryl-fnnctionalized vanadyl(IV) salen complexes (nonchiral and chiral versions) were covalently anchored onto mercapto-modified ACs and SWCNTs 

2-mercaptoethylamine. The mercapto-fnnctionalized SWCNTs and ACs were then linked to the vanadyl complex throngh a radical chain addition of the mer-capto gronp to the terminal functional C=C group of the complex, initiated by AIBN (2,2 -azobisisobutyronitrile) the modified SWCNTs were more efficient in anchoring the yO(salen)] complex (Fignre 8.9). 

The Rh complex [Rh(cod)(diphosphine)], with diphosphine ligands functionalized with hydroxyls groups, was immobilized onto several ACs and carbon cloth with different textural chemistry previously modified with the spacer naph-toic acid the materials were characterized by gas adsorption, TPD, and TG-DSC 

SWCNTs were modified with several water-soluble pyrene derivatives (1-pyreneacetic acid, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, and 8-hydroxy-l,3,6-pyrenetrisulfonic acid) bearing negatively charged ionic head-groups, to act as anchors to several pyridium headgroups present in a series of water-soluble metalloporphyrins [MP] + (M = Zn, Co, and Fe) [60a]. Interactions between the metalloporphyrins and SWCNTs proceeded through a combination of associative van der Waals (spacer-CNT) and electrostatic interactions (metalloporphyrins-spacer-CNT), as demonstrated by the combination of spectroscopic and surface techniques. 

A pyrene derivative was also used as an anchor to immobilize a ruthenium alkylidene complex onto SWCNTs [94]. The immobilization of the Ru complex was performed by two different paths (1) adsorption of pyrene derivative precursor onto the sidewall of nanotubes by ti-ti interactions, followed by cross-metathesis with the ruthenium alkylidene complex, and (2) adsorption onto the sidewall of SWCNTs of the pyrene-substituted ruthenium alkylidene prepared previously. 

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