As the active site models of FeFe-hydrogenases, a series of new diiron propanedithiolate compounds (1-7) have been synthesized starting from [(μ-SCH 2 ) 2 CH(OH)]Fe 2 (CO) 6 (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine gave the malonyl-containing compounds [(μ-SCH 2 ) 2 CHO 2 CCH 2 CO 2 Et]Fe 2 (CO) 6 (1) and [Fe 2 (CO) 6 (μ-SCH 2 ) 2 CHO 2 C] 2 CH 2 (2) in 64% and 55% yields, respectively. While A reacted with PPh 3 in the presence of Me 3 NO to give the PPh 3 -substituted compound [(μ-SCH 2 ) 2 CH(OH)]Fe 2 (CO) 5 (PPh 3 ) (3) in 91% yield, reaction of 3 with malonyl dichloride in the presence of pyridine produced the malonyl-containing compound [Fe 2 (CO) 5 (PPh 3 )(μ-SCH 2 ) 2 CHO 2 C] 2 CH 2 (4) in 67% yield. More interestingly, compounds 1, 2, and 4 could react with C 60 in the presence of CBr 4 and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to afford the [60]fullerene compounds [(μ-SCH 2 ) 2 CHO 2 CC(C 60 )CO 2 Et]Fe 2 -(CO) 6 (5), [Fe 2 (CO) 6 (μ-SCH 2 ) 2 CHO 2 C] 2 C(C 60 ) (6), and [Fe 2 (CO) 5 (PPh 3 )(μ-SCH 2 ) 2 CHO 2 C] 2 C(C 60 ) (7) in 36-39% yields. While new compounds 1-7 were characterized by elemental analysis and various spectroscopic methods, 1-4 were further characterized by X-ray crystallography, and the photoinduced H 2 evolution catalyzed by 5 was preliminarily investigated.

Diverse nanostructures and nano-objects for advanced applications are created by the self-assembly of lipids, surfactants, and block copolymers. Understanding this process is critical for improving their functions and expanding their applications. Accordingly, we pioneered the synthesis and application of heterocluster Janus molecules (HCJMs), which resemble conventional amphiphiles. Their self-assembly into nanostructures and nano-objects can be directly characterized by transmission electron microscopy (TEM), allowing the process to be unraveled through the monitoring of the intermediates. In this study, we focused on the TEM characterization of HCJM-based colloidal onions, which have an onion-like inner structure, to gain insight into the self-assembly process from molecules to perfect onions. Multiple mechanisms, including molecular aggregation, structural ordering within aggregates into colloidal onions, and layer-by-layer growth caused by particle coarsening, contributed to the overall self-assembly process. The analysis also indicated that the reduction in the Gibbs free energy and bending free energy of curved layers are the driving forces for structural ordering and onion growth. Finally, this work provided a useful method for preparing colloidal onions for attractive applications in nanomedicine and other areas.

A series of new diiron azadithiolate (ADT) complexes (1-8), which could be regarded as the active site models of [FeFe]hydrogenases, have been synthesized starting from parent complex [(μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine afforded the malonyl-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6) (1) and [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (2). Further treatment of 1 and 2 with PPh(3) under different conditions produced the PPh(3)-substituted complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (3), [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(4)(PPh(3))(2) (4), and [Fe(2)(CO)(5)(PPh(3))(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (5). More interestingly, complexes 1-3 could react with C(60) in the presence of CBr(4) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to give the C(60)-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60)) (7), and [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (8). The new ADT-type models 1-8 were characterized by elemental analysis and spectroscopy, whereas 2-4 were further studied by X-ray crystallography and 6-8 investigated in detail by DFT methods.

The first phosphinobenzaldehyde- and phosphinoporphyrin-functionalized model complexes (1–4) have been synthesized and structurally characterized. Thus, reaction of diiron complex [(μ-SCH2)2CH2]Fe2(CO)6 or [(μ-SCH2)2NC6H4CO2Me-p]Fe2(CO)6 with p-Ph2PC6H4CHO in the presence of Me3NO gave the phosphinobenzaldehyde-functionalized model complexes [(μ-SCH2)2CH2]Fe2(CO)5(p-Ph2PC6H4CHO) (1) and [(μ-SCH2)2NC6H4CO2Me-p]Fe2(CO)5(p-Ph2PC6H4CHO) (2) in 61% and 71% yields, respectively. Further reaction of 1 or 2 with PhCHO, pyrrole, and BF3·OEt2 followed by treatment with p-chloranil resulted in formation of the phosphinoporphyrin-functionalized model complexes 5-{[(μ-SCH2)2CH2]Fe2(CO)5(p-Ph2PC6H4)}-10,15,20-triphenylporphyrin (3) and 5-{[(μ-SCH2)2NC6H4CO2Me-p]Fe2(CO)5(p-Ph2PC6H4)}-10,15,20-triphenylporphyrin (4) in 19% and 18% yields, respectively. While the new complexes 1–4 were characterized by elemental analysis and spectroscopy, the structures of 1, 3, and 4 were confirmed by X-ray crystallography. Particularly interesting is that complex 4 was found to be a catalyst for the photoinduced H2 production in the presence of the electron donor EtSH and the proton source HOAc.

The butterfly Fe/S cluster anions (µ-RS)(µ-S -)Fe 2 (CO) 6 (A, R ) Et, p-MeC 6 H 4 ), (µ-S -) 2 Fe 2 (CO) 6 (C), [(µ-S -)Fe 2 (CO) 6 ] 2 (4-µ-SC 6 H 4 C 6 H 4 S-µ-4′) (D), and [(µ-S -)Fe 2 (CO) 6 ] 2 [4-µ-SC 6 H 4 OCH 2 CH 2 OC 6 H 4 Sµ-4′] (E) (generated in situ via reactions of (µ-S 2 )Fe 2 (CO) 6 with RMgBr, Et 3 BHLi, 4-LiC 6 H 4 C 6 H 4 Li-4′, and 4-LiC 6 H 4 OCH 2 CH 2 OC 6 H 4 Li-4′) were found to react with Ph 2 PCl to give a series of novel butterfly Fe/S/P cluster complexes. Treatment of monoanions A (R ) Et, p-MeC 6 H 4 ) with 1 equiv of Ph 2 PCl in THF from -78 °C to room temperature gave the single-butterfly Fe 2 S 2, whereas dianions C, D, and E reacted with 2 equiv of Ph 2 PCl to give single-butterfly Fe 2 S 2 P 2 complex (η 1 -Ph 2 PS-η 1 ) 2 Fe 2 (CO) 6 ( 11) and double-butterfly Fe 4 S 4 P 2 complexes [(η 1 -Ph 2 PS-η 1 )Fe 2 (CO) 6 ] 2 (4-µ-SC 6 H 4 C 6 H 4 S-µ-4′) ( 12) and [(η 1 -Ph 2 PS-η 1 )Fe 2 (CO) 6 ] 2 [4-µ-SC 6 H 4 OCH 2 CH 2 OC 6 H 4 S-µ-4′] (13), respectively. More interestingly, the novel µ 4 -S-containing doublebutterfly Fe 4 S 2 P complexes [(µ-RS)Fe 2 (CO) 6 ](µ 4 -S)[(µ-Ph 2 P)Fe 2 (CO) 6 ] (14, R ) Me; 15, R ) Ph; 16, R ) Et) could be prepared by reactions of single-butterfly complexes (µ-RS)(η 1 -Ph 2 PS-η 1 )Fe 2 (CO) 6 (1, R ) Me; 3, R ) Ph; 7 R ) Et) with excess Fe 2 (CO) 9 in THF at room temperature, whereas the quadruplebutterfly Fe 8 S 4 P 2 complexes [(µ-Ph 2 P)Fe 2 (CO) 6 (µ 4 -S)Fe 2 (CO) 6 ] 2 (4-µ-SC 6 H 4 C 6 H 4 S-µ-4′) ( 17) and [(µ-Ph 2 P)Fe 2 (CO) 6 (µ 4 -S)Fe 2 (CO) 6 ] 2 [4-µ-SC 6 H 4 OCH 2 CH 2 OC 6 H 4 S-µ-4′] (18) were similarly prepared by reactions of the corresponding double-butterfly complexes 12 and 13 with excess Fe 2 (CO) 9 , respectively. All the new complexes 7-18 have been characterized by elemental analysis, by spectroscopy, and for 9, 11, and 14 by X-ray crystallography. In view of the structural similarity of these Fe/S/P complexes to the [FeFe]-hydrogenase active site, they might be regarded as H-cluster models. As a representative, model complex 11 was found to be able to catalyze proton reduction to hydrogen under CV conditions.