Journal
DALTON TRANSACTIONS
Volume 41, Issue 42, Pages 13060-13073Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt30309d
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Funding
- Student Research Participation Program at the U.S. Army Engineer Research and Development Center, Construction Engineering Research Laboratory
- Center Directed Research Program at the U.S. Army Corps of Engineers
- Arnold and Mabel Beckman Foundation
- Mississippi LSAMP [HRD-0602740]
- Mississippi INBRE
- National Center for Research Resources [5P20RR016476-11]
- National Institute of General Medical Sciences from the National Institutes of Health [8 P20 GM103476-11]
- National Science Foundation (NSF) [CHE 0639208]
- NSF CRIF:MU Award [0741991, 0840390]
- NSF [CHE - 1151832]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0741991, 0840390] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1151832] Funding Source: National Science Foundation
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We report the synthesis and characterization of novel mixed-metal binuclear ruthenium(II)-cobalt(II) photocatalysts for hydrogen evolution in acidic acetonitrile. First, 2-(2'-pyridyl)benzothiazole (pbt), 1, was reacted with RuCl3 center dot xH(2)O to produce [Ru(pbt)(2)Cl-2]center dot 0.25CH(3)COCH(3), 2, which was then reacted with 1,10-phenanthroline-5,6-dione (phendione), 3, in order to produce [Ru(pbt)(2)(phendione)](PF6)(2)center dot 4H(2)O, 4. Compound 4 was then reacted with 4-pyridinecarboxaldehyde in order to produce [Ru(pbt)(2)(L-pyr)]-(PF6)(2)center dot 9.5H(2)O, 5 (where L-pyr = (4-pyridine) oxazolo[4,5-f]phenanthroline). Compound 5 was then reacted with [Co(dmgBF(2))(2)(H2O)(2)] (where dmgBF(2) = difluoroboryldimethylglyoximato) in order to produce the mixed-metal binuclear complex, [Ru(pbt)(2)(L-pyr) Co(dmgBF(2))(2)(H2O)](PF6)(2)center dot 11H(2)O center dot 1.5CH(3)COCH(3), 6. [Ru(Me(2)bpy)(2)(L-pyr) Co(dmgBF(2))(2)(OH2)](PF6)(2), 7 (where Me(2)bpy = 1,10-phenanthroline, 4,4'-dimethyl-2,2'-bipyridine) and [Ru(phen)(2)(L-pyr) Co(dmgBF(2))(2)(OH2)](PF6)(2), 8 were also synthesised. All complexes were characterized by elemental analysis, ESI MS, HRMS, UV-visible absorption, B-11, F-19, and Co-59 NMR, ESR spectroscopy, and cyclic voltammetry, where appropriate. Photocatalytic studies carried out in acidified acetonitrile demonstrated constant hydrogen generation longer than a 42 hour period as detected by gas chromatography. Time resolved spectroscopic measurements were performed on compound 6, which proved an intramolecular electron transfer from an excited Ru(II) metal centre to the Co(II) metal centre via the bridging L-pyr ligand. This resulted in the formation of a cobalt(I)-containing species that is essential for the production of H-2 gas in the presence of H+ ions. A proposed mechanism for the generation of hydrogen is presented.
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