Pillar substitution in a long-known metal-organic material with saturated metal centres, [Cu(bipy)(2)(SiF(6))](n), has afforded the first crystallographically characterized porous materials based upon TiF(6)(2-) and SnF(6)(2-) anions as pillars. Gas adsorption studies revealed similar surface areas and adsorption isotherms but enhanced selectivity towards CO(2)vs. CH(4) and N(2).
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