Synthesis and characterization of mono- and dinuclear phenanthroline-extended tetramesitylporphyrin complexes as well as UV-Vis and EPR studies on their one-electron reduced species

被引:20
作者
Matlachowski, Corinna [1 ]
Schwalbe, Matthias [1 ]
机构
[1] Humboldt Univ, Inst Chem, D-12489 Berlin, Germany
关键词
PORPHYRIN-CATALYZED REDUCTION; RUTHENIUM COMPLEX; BRIDGING LIGAND; WATER OXIDATION; HYDROGEN; ENERGY; DELOCALIZATION; PHOTOOXIDATION; CHALLENGES; ALCOHOLS;
D O I
10.1039/c2dt32196c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The syntheses of mononuclear compounds based on the fused porphyrin phenanthroline ligand (H-2-1) and their corresponding dinuclear porphyrin bis-bipyridine ruthenium complexes are reported. The extended pi-system of the ligand is able to store electron equivalents as could be proven by the single electron reduction with KC8 (and/or Na(Hg)) followed by subsequent UV-Vis and EPR analysis. Electron reduction could also be achieved under light illumination in a dichloromethane-triethylamine mixture. The two coordination spheres of the ligand are different so that mononuclear or (hetero) dinuclear complexes can be isolated depending on the reaction conditions. We could successfully introduce Zn, Cu and Pd into the porphyrinic unit leading to a series of mononuclear (M-1) compounds. Further, we could attach the bis-(4,4'-di-tert-butyl-2,2'-bipyridine) ruthenium fragment (Ru(tbbpy)(2)(2+)) to obtain dinuclear (M-1-Ru) metal complexes. In the case of Zn-1 an X-ray crystal structure could be obtained confirming the selective metallation in the porphyrinic unit. All metal complexes were isolated and characterized with standard analytical tools (elemental analysis, mass spectrometry and NMR (or EPR) spectroscopy).
引用
收藏
页码:3490 / 3503
页数:14
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共 57 条
[1]   The future of energy supply: Challenges and opportunities [J].
Armaroli, Nicola ;
Balzani, Vincenzo .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (1-2) :52-66
[2]   A study on the oxidation of 2-hydroxyporphyrins to porphyrin-α-diones [J].
Beavington, R ;
Rees, PA ;
Burn, PL .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1998, (17) :2847-2851
[3]   Cobalt porphyrin catalyzed reduction of CO2.: Radiation chemical, photochemical, and electrochemical studies [J].
Behar, D ;
Dhanasekaran, T ;
Neta, P ;
Hosten, CM ;
Ejeh, D ;
Hambright, P ;
Fujita, E .
JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (17) :2870-2877
[4]   Homogeneous catalysis of electrochemical hydrogen evolution by iron(0) porphyrins [J].
Bhugun, I ;
Lexa, D ;
Saveant, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (16) :3982-3983
[5]   Synthesis of free and ruthenium coordinated 5,6-diamino-1,10-phenanthroline [J].
Bodige, S ;
MacDonnell, FM .
TETRAHEDRON LETTERS, 1997, 38 (47) :8159-8160
[6]   Catalytic Photooxidation of Alcohols by an Unsymmetrical Tetra(pyridyl)pyrazine-Bridged Dinuclear Ru Complex [J].
Chen, Weizhong ;
Rein, Francisca N. ;
Scott, Brian L. ;
Rocha, Reginaldo C. .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (20) :5595-5604
[7]   Homogeneous Photocatalytic Oxidation of Alcohols by a Chromophore-Catalyst Dyad of Ruthenium Complexes [J].
Chen, Weizhong ;
Rein, Francisca N. ;
Rocha, Reginaldo C. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (51) :9672-9675
[8]   Ultrafast processes in bimetallic dyads with extended aromatic bridges. Energy and electron transfer pathways in tetrapyridophenazine-bridged complexes [J].
Chiorboli, C ;
Rodgers, MAJ ;
Scandola, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (02) :483-491
[9]   Making Oxygen with Ruthenium Complexes [J].
Concepcion, Javier J. ;
Jurss, Jonah W. ;
Brennaman, M. Kyle ;
Hoertz, Paul G. ;
Patrocinio, Antonio Otavio T. ;
Murakami Iha, Neyde Yukie ;
Templeton, Joseph L. ;
Meyer, Thomas J. .
ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (12) :1954-1965
[10]   Catalytic and Surface-Electrocatalytic Water Oxidation by Redox Mediator-Catalyst Assemblies [J].
Concepcion, Javier J. ;
Jurss, Jonah W. ;
Hoertz, Paul G. ;
Meyer, Thomas J. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (50) :9473-9476