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Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts
Author(s) -
Koutsouri Eugenia,
Zarkadoulas Athanasios,
Kefalidi Christina,
Papatriantafyllopoulou Constantina,
Mitsopoulou Christiana A.
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900886
Subject(s) - chemistry , catalysis , reactivity (psychology) , triethanolamine , nickel , photocatalysis , ligand (biochemistry) , cyclic voltammetry , acetic acid , medicinal chemistry , infrared spectroscopy , crystal structure , crystallography , inorganic chemistry , electrochemistry , organic chemistry , analytical chemistry (journal) , medicine , biochemistry , alternative medicine , receptor , electrode , pathology
Herein, we present an artificial photocatalytic system for H 2 evolution based on a series of proton reduction catalysts, namely [Ni{S 2 C 2 (Ph) 2 } 2 ] ( 1 ), [Ni{S 2 C 2 (Ph) 2 } 2 ](NEt 4 ) ( 1 – ), [Ni{S 2 C 2 (Ph)(Ph–OCH 3 ‐4)} 2 ] ( 2 ), [Ni{S 2 C 2 (Ph)(Ph–OCH 3 ‐4)} 2 ](NEt 4 ) ( 2 – ), [Ni{S 2 C 2 (Ph–OCH 3 ‐4) 2 } 2 ] ( 3 ) and [Ni{S 2 C 2 (Ph–OCH 3 ‐4) 2 } 2 ](NEt 4 ) ( 3 – ), [Ni(mnt) 2 ] (NBu 4 ) ( 4 – ), [Ni(mnt)(S 2 C 2 (Ph) 2 )](NBu 4 ) ( 5 – ). These complexes are different of both in charge and the substituents on dithiolene ligand and represent a group of active catalysts for the reduction of protons with high TONs. A series of Re I complexes, [ReBr(CO) 3 (bpy)], [ReCl(CO) 3 (bpy)], [Re(NCS)(CO 3 )(bpy)], [ReBr(CO) 3 (amphen)] and [ReBr(CO) 3 (pq)] were used as photosensitizers, in combination with triethanolamine as a sacrificial electron donor and acetic acid as a proton source. The differences of the ligands in the electron donating properties and reactivity are discussed in the light of the experimental data. We also present the physicochemical characterization of a previously reported heteroleptic monoanionic complex ( 5 – ), by UV/Vis spectroscopy, FTIR spectroscopy, cyclic voltammetry and single‐crystal X‐ray diffraction studies.