Self-Assembly of a Hierarchical Metal-Organic Framework at the Liquid/Liquid Interface via π-π Stacking Manipulations in Organoplatinum(IV) Complexes for Methanol Fuel Cells.

This study focuses on the facile synthesis of the hierarchical architecture of zeolitic imidazolate framework-8 (ZIF-8) films containing an ultrasmall amount of Pt(0) by investigating the synthesis of different organoplatinum complexes and manipulating the π-π stacking effect in these complexes at the liquid/liquid interface. The organometallic Pt(IV) precursors were complexes with a formula of [PtXMe(R)(bpy)] (bpy = 2,2'-bipyridine; for complex , R = CHCH═CHCH and X = Br; for complex , R = CHCH═CH and X = Br; for complex , R = Me and X = I) prepared by oxidative addition of cinnamyl bromide, allyl bromide, or methyl iodide to [PtMe(bpy)] (complex ). Different thin films were synthesized starting from three organometallic Pt(IV) precursors (i) by reduction of the Pt complexes at the toluene/water interface (-), (ii) by encapsulation of the Pt precursors in a ZIF-8 (-), and (iii) by reduction of the Pt precursors onto a ZIF-8 (-).