[Fe 2 S 2 -Ag x ]-Hydrogenase Active-Site-Containing Coordination Polymers and Their Photocatalytic H 2 Evolution Reaction Properties.

Three [Fe 2 S 2 -Ag x ]-hydrogenase active-site-containing coordination polymers (CPs), {[Fe 2 S 2 -Ag 1 ](4-cpmt) 2 (CO) 6 (ClO 4 - )} n ( 1 ), {[Fe 2 S 2 -Ag 2 ](4-cpmt) 2 (CO) 6 (OTf - ) 2 (benzene)} n ( 2 ), and {[Fe 2 S 2 -Ag 2 ](3-cpmt) 2 (CO) 6 (ClO 4 - ) 2 } n ( 3 ), were obtained by a direct synthesis method from ligands [FeFe](4-cpmt) 2 (CO) 6 [ L1 ; 4-cpmt = (4-cyanophenyl)methanethiolate] and [FeFe](3-cpmt) 2 (CO) 6 [ L2 ; 3-cpmt = (3-cyanophenyl)methanethiolate] with silver salts. 1 - 3 represent the first examples of [FeFe]-hydrogenase-based CPs. It was worth noting that the Ag-S bonding between the Ag centers and S atoms of a [Fe 2 S 2 ] cluster produced a novel [Fe 2 S 2 -Ag x ] ( x = 1 or 2) catalytic site in all three polymers. The results of photochemical H 2 generation experiments indicated that 2 and 3 containing [Fe 2 S 2 -Ag 2 ] active sites showed obviously improved catalytic performances compared with ligands L1 and L2 and [Fe 2 S 2 -Ag 1 ]-containing 1 . This work provides a pioneering strategy for the direct synthesis of [Fe 2 S 2 ]-based CPs or metal-organic frameworks.