Chi-Chiu Ko

Transition metal complexes with photochromic ligands - Photosensitization and photoswitchable properties

The development of transition metal complexes with ligands containing different photochromic families has received increasing attention in recent years. Through rational design of the photochromic moieties as ligands, the photochromic properties could be systematically perturbed and varied by relatively simple coordination to different metal centres. In this article, a number of examples, in particular those ligands containing stilbenes, azo compounds, spirooxazines and diarylethenes, are selected to demonstrate the design, perturbation and photosensitization of photochromic moieties with transition metal–ligand chromophores. The photoswitching properties of the transition metal complex functionality are described.

Photochromic Diarylethene-Containing Ionic Liquids and N-Heterocyclic Carbenes

The design and synthesis of a series of photochromic diarylethene-containing Arduengo-type N-heterocyclic carbenes (NHCs) of gold(I), silver(I) and palladium(II) and their imidazolium salt precursors are reported. Reversible photochromic behavior was observed. The open form and the closed form also show different luminescence properties. The electronic and conformational/steric changes associated with the photocyclization and photocycloreversion reactions may open up new opportunities for the discovery of new classes of photochromic ligands and metal-containing materials and catalysts with photoswitchable functions and activities and regio-/enantioselectivities.

Cerium(IV)-Driven Water Oxidation Catalyzed by a Manganese(V)–Nitrido Complex†

The study of manganese complexes as water-oxidation catalysts (WOCs) is of great interest because they can serve as models for the oxygen-evolving complex of photosystem II. In most of the reported Mn-based WOCs, manganese exists in the oxidation states III or IV, and the catalysts generally give low turnovers, especially with one-electron oxidants such as Ce(IV) . Now, a different class of Mn-based catalysts, namely manganese(V)-nitrido complexes, were explored. The complex [Mn(V) (N)(CN)4 ](2-) turned out to be an active homogeneous WOC using (NH4 )2 [Ce(NO3 )6 ] as the terminal oxidant, with a turnover number of higher than 180 and a maximum turnover frequency of 6 min(-1) . The study suggests that active WOCs may be constructed based on the Mn(V) (N) platform.

Luminescent rhenium(I) complexes with acetylamino- and trifluoroacetylamino-containing phenanthroline ligands: anion-sensing study.

A series of rhenium complexes with acetylamino- and trifluoroacetylamino-containing 1,10-phenanthroline ligands have been synthesized, characterized and their photophysical and electrochemical properties studied. These complexes were found to show significant UV-vis and emission changes on addition of CN(-), F(-) and AcO(-) anions. Their reactivity towards CN(-), F(-) and AcO(-) anions, was also investigated by UV-vis, emission and (1)H NMR spectroscopy. The reaction product between the trifluoroacetylamino-containing 1,10-phenanthroline ligand and the CN(-) anion has also been structurally characterized by X-ray crystallography.

Syntheses, characterization, and photochromic studies of spirooxazine-containing 2,2′-bipyridine ligands and their zinc(II) thiolate complexes

A series of photochromic spirooxazine-containing zinc(II) diimine bis-thiolate complexes were successfully synthesized, and their photophysical and photochromic properties were studied. The X-ray crystal structure of complex 1a has also been determined. Upon excitation by UV light at 330 nm, all the ligands and complexes exhibit photochromic behavior. The thermal bleaching kinetics of the ligands and the complexes were studied in dimethylformamide at various temperatures. The photochemical quantum yields for the photochromic reactions of the ligands and complexes were also determined.

Synthesis, characterization, and photophysical study of luminescent rhenium(I) diimine complexes with various types of N-heterocyclic carbene ligands.

A series of luminescent Re(I) diimine complexes with various types of N-heterocyclic carbene (NHC) ligands has been synthesized through the reaction between isocyano Re(I) diimine complexes with different nucleophiles. These Re(I) NHC complexes were characterized by (1)H and (13)C NMR and IR spectroscopy, mass spectrometry, and elemental analysis. One of the precursor complexes fac-{Re(CO)3[CN(H)C6H4-2-O]2Br} and five of the Re(I) diimine complexes with different types of NHC ligands were also structurally characterized by X-ray crystallography. In the preparation of these Re(I) NHC complexes, it is found that the reactivity of the isocyanide ligands in the synthetic complex precursors is significantly affected by the electronic nature of the trans ligand. All these complexes displayed (3)MLCT [dπ(Re) → π*(N-N)] phosphorescence in degassed CH2Cl2 and CH3CN solutions at room temperature. Through the study of the photophysical and electrochemical properties of these Re(I) NHC complexes, the electronic properties of different types of NHC ligands were investigated.

A new class of highly solvatochromic dicyano rhenate(I) diimine complexes – synthesis, photophysics and photocatalysis

A new class of dicarbonyl dicyano rhenate(I) diimine complexes, cis,trans-[Re(CO)(2)(CN)(2)(N-N)](-), with highly environmentally sensitive MLCT absorption and emission properties was synthesised and characterised. Preliminary experiments revealed that these complexes are active photocatalysts for CO(2) reduction.

Synthesis, characterisation and photophysical studies of leucotriarylmethanes-containing ligands and their rhenium(I) tricarbonyl diimine complexes

A series of pyridine- and bipyridine-containing leucotriarylmethane ligands has been successfully synthesised and incorporated into tricarbonyl rhenium(I) diimine complexes. The X-ray crystal structures of two of the complexes have also been determined. The photoreactivity, photophysical and electrochemical properties of these ligands and their rhenium complexes were investigated. The photo-ionisation of the leucotriarylmethanes in the free ligands and their metal complexes and the subsequent change in absorption properties were also studied. Additionally, the electrochemistry of these ligands and complexes were investigated.

Coordination Compounds with Photochromic Ligands: Ready Tunability and Visible Light-Sensitized Photochromism

Photochromic compounds are well-known for their promising applications in many areas. In this context, many different photochromic families have been developed. As the early study of these photochromic compounds was mainly focused on the organic system, their photochromic reactivity was mainly derived from the singlet excited state. We hypothesized that the incorporation of the photochromic ligand to the transition metal complex and coordination complex systems would not only render the triplet state of the organic photochromic system more readily accessible due to the large spin-orbit coupling of the heavy metal center but also would lead to ready extension of the excitation wavelength to less destructive longer wavelength low-energy excitation. On the other hand, the long-lived triplet excited states of the metal complexes are also suitable for energy or electron transfer processes, which should lead to new photochromic behavior and photoswitchable functional properties. Through the incorporation of the stilbene-, azo-, spirooxazine-, and dithienylethene-containing ligands to transition metal complex systems with heavy metal centers and suitable excited states, triplet state photosensitized photochromism has been achieved. With the triplet state photosensitization, the photochromism of these compounds could be extended from the high energy UV region to the visible region. In the development of dithienylethene-containing ligands, we have adopted an alternative strategy, which involves the incorporation of nitrogen and sulfur heterocycles that directly form part of the dithienylethene framework as ligands to exert a much stronger perturbation and influence on the excited state properties of the photochromic unit by the metal center. On the basis of the new design, wide ranges of dithienylethene-containing ligands, including phenanthrolines, 2-pyridylimidazoles, N-pyridylimidazol-2-ylidenes, cyclometalating thienylpyridines, β-diketonates, and β-ketoiminates have been designed and incorporated into various coordination systems. Apart from the photosensitization, tuning of the closed form absorption and photochromic behavior based on the perturbation of the metal center, coordination-assisted planarization, modification of the ancillary ligands and introduction of various electronic excited states derived from the coordination system have been successfully demonstrated. This strategy can be used for developing NIR photochromic dithienylethenes. With the above effects observed upon the coordination to different transition metal centers and central atoms, this strategy offers a simple and effective way for the modification of the photochromic characteristics. Moreover, the emission and other functional properties of the coordination systems could also be photoswitched by the photochromic reactions.

Luminescent Rhenium(I) Pyridyldiaminocarbene Complexes: Photophysics, Anion-Binding, and CO2-Capturing Properties.

A series of luminescent isocyanorhenium(I) complexes with chelating acyclic diaminocarbene ligands (N^C) has been synthesized and characterized. Two of these carbene complexes have also been structurally characterized by X-ray crystallography. These complexes show blue-to-red phosphorescence, with the emission maxima not only considerably varied with a change in the number of ancillary isocyanide ligands but also extremely sensitive to the electronic and steric nature of the substituents on the acyclic diaminocarbene ligand. A detailed study with the support of density functional theory calculations revealed that the lowest-energy absorption and phosphorescence of these complexes in a degassed CH2Cl2 solution are derived from the predominantly metal-to-ligand charge-transfer [dπ(Re) → π*(N^C)] excited state. The unprecedented anion-binding and CO2-capturing properties of the acyclic diaminocarbene have also been described.