Chemical approaches to artificial photosynthesis

Meyer, Thomas J.

doi:10.1021/ar00161a001

Cited by 1,313 publications

(902 citation statements)

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“…Hence it can be concluded that the dominant interaction in the mixed valence state of 4 is that of a dp(M III )-p(L) 5 mixing with p-orbitals of the bridging ligand (HOMO mediated superexchange). 17 By comparison of the reduction potentials of 4 with those of 1 and 2 (Fig.…”

Section: Comparison Of Bpypytr Bridged Complexes 3-5 50mentioning

confidence: 99%

“…Metal complexes based on polypyridyl ligands constitute versatile components for the construction of multifunctional supramolecular systems in molecular photonics and molecular electronics, 1 sensors, 2 photocatalysis, 3 solar energy 5 conversion, 4 artificial photosynthesis, 5 non-linear optics, 6 and electrochemoluminescence 7 amongst others. 8, 9 The myriad of applications are founded on the well defined chemistry of these compounds and take advantage of the versatile photophysical, 10 photochemical 11 and electrochemical 12 properties that are associ-10 ated with the metal-to-ligand charge-transfer (MLCT) excitation in these metal complexes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

et al. 2009

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A series of binuclear ruthenium and osmium complexes [(bipy) (5) and [(bipy) 2 Os(bpbt)Os(bipy) 2 ] 2+ (6) {bipy = 2,2¢-bipyridyl; qpy = 2,2¢:5¢,5¢¢:2¢¢,2¢¢¢-quaterpyridyl; pytr-bipy = 3-(2,2¢-bipyrid-6-yl)-5-(pyrid-2-yl)-1,2,4-triazolato, and bpbt = 5,5¢-bis-(pyrid-2¢¢-yl)-3,3¢-bis-1,2,4-triazolato} are reported. Analysis of the electrochemical data focuses on structural factors and on determining the extent of electronic communication between the metal centres in the mixed valence oxidation state. Intervalence charge transfer (IT) bands could be identified in the spectra of the complexes 4 and 6 only. Analysis of their spectroelectrochemical data leads to the conclusion that the IT is superexchange mediated through the HOMO of the bridging ligand. IntroductionMetal complexes based on polypyridyl ligands constitute versatile components for the construction of multifunctional supramolecular systems in molecular photonics and molecular electronics, 1 sensors, 2 photocatalysis, 3 solar energy 5 conversion, 4 artificial photosynthesis, 5 non-linear optics, 6 and electrochemoluminescence 7 amongst others. 8, 9 The myriad of applications are founded on the well defined chemistry of these compounds and take advantage of the versatile photophysical, 10 photochemical 11 and electrochemical 12 properties that are associ-10 ated with the metal-to-ligand charge-transfer (MLCT) excitation in these metal complexes. 13 Amongst the many multinuclear polypyridyl complexes reported, 14 an interesting subclass is represented by those binuclear systems that display additional spectroelectrochemical features 15 due to the electronic interaction between the two metal centres in the mixed valence redox state(s). 15,16 "Communication" between metal centres where direct overlap of atomic orbitals is not possible is achieved when the bridging ligand (BL) has a system of polarisable electrons that are capable of mediating 20 the redistribution of the electronic charge between the two metal centres. Sciences, Dublin City University, Dublin 9, Analysis of these absorption bands 25 can provide detailed information as to the nature and extent of the interaction between the metals centres. 30 Recently, we reported the synthesis and characterisation of a series of homo-and hetero-binuclear ruthenium(II) and osmium(II) complexes of the general formula [M 1 (bipy) 2 -BL-M 2 (bipy) 2 ], where M = Ru or Os, bipy is 2,2¢-bipyridyl (bipy), and BL the bridging ligands 2,2¢:5¢,5¢¢:2¢¢,2¢¢¢-quaterpyridyl (qpy), 3-(2,2¢-35 bipyrid-6-yl)-5-(pyrid-2-yl)-1,2,4-triazolato (pytr-bipy), and 5,5¢-bis-(pyrid-2¢¢-yl)-3,3¢-bis-1,2,4-triazolato (bpbt). 26 In the present contribution, we describe in detail the electrochemical and spectroelectrochemical properties of these compounds. The goal of the present study is to evaluate the extent 40 of electronic communication between the two metal centres as a function of the electronic properties of the bridging ligand and the positioning of the two metal centres. In particular, attention is directed towards the hom...

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Section: Comparison Of Bpypytr Bridged Complexes 3-5 50mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

et al. 2009

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“…Mention will be made both of biological systems and heterogeneous systems where appropriate, but these are not the focus of this review. A number of related reviews [15][16][17][18][19][20][21][22] have appeared.…”

Section: Introductionmentioning

confidence: 99%

Functional models for the oxygen-evolving complex of photosystem II

Cady

Crabtree

Brudvig

2008

Coordination Chemistry Reviews

387

255

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In the last ten years, a number of advances have been made in the study of the oxygen-evolving complex (OEC) of photosystem II (PSII). Along with this new understanding of the natural system has come rapid advance in chemical models of this system. The advance of PSII model chemistry is seen most strikingly in the area of functional models where the few known systems available when this topic was last reviewed has grown into two families of model systems. In concert with this work, numerous mechanistic proposals for photosynthetic water oxidation have been proposed. Here, we review the recent efforts in functional model chemistry of the oxygen-evolving complex of photosystem II.

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“…The Emission spectra of ligand L 1 and its metal complex L 3 in chloroform at room temperature is shown in Figure 3 and Figure 4 and the relevant data are collected in Table 1. The luminescence of the ligands L 1 , L 2 and L 3 are assigned to the benzothiazolyl hydrazone centered л-л* level [34][35][36][37] . The ligands L 1 , L 2 and L 3 showed the emission bands at 532 nm, 545 nm and 542 nm respectively.…”

Section: Uv-vis Absorption Spectra and Emission Spectramentioning

confidence: 99%

Synthesis and Spectroscopic Characterization of Some Novel Polypyridine and Phenanthroline Complexes of Mn(II), Fe(II), Co(II) and Zn(II) Incorporating a Bidentate Benzothiazolyl Hydrazone Ligand

2013

Chem Sci Trans

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Eight novel polypyridine and phenanthroline complexes of Mn(II), Fe(II), Co(II) and Zn(II) (1-8) of the type [M(N-N) 2 (L)]Cl 2 where N-N is 2,2'-bipyridine (bpy) 2 and 1,10-phenanthroline (phen) 2 with three benzothiazolyl hydrazone ligands L 1 -L 3 were synthesized and characterized by elemental analysis, thermal conductance, UV-Vis, IR, 1 H NMR, electronic absorption and emission spectral methods. The IR, 1 H NMR, electronic absorption and emission spectral data revealed that the ligands coordinate with the metal ions in a bidentate fashion through azomethine nitrogen and phenolic oxygen to form complexes. The analytical and thermogravimetrical data correlated with the observations from IR, 1 H NMR, electronic absorption and emission spectra permitted to attribute that the metal ions are six coordinated in all the complexes.

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Chemical approaches to artificial photosynthesis

Cited by 1,313 publications

References 76 publications

Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

Functional models for the oxygen-evolving complex of photosystem II

Synthesis and Spectroscopic Characterization of Some Novel Polypyridine and Phenanthroline Complexes of Mn(II), Fe(II), Co(II) and Zn(II) Incorporating a Bidentate Benzothiazolyl Hydrazone Ligand

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