Jin Yun Wang

Electrical conductance study on 1,3-butadiyne-linked dinuclear ruthenium(II) complexes within single molecule break junctions

Single-molecule conductance of three sulphur-functionalized organometallic wires with two ruthenium(II) centres spaced by 1,3-butadiyne was firstly investigated using an electrochemically assisted-mechanically controllable break junction (EC-MCBJ) approach. It is demonstrated that single-molecular conductance of these diruthenium(II) incorporated systems is significantly higher than oligo(phenylene-ethynylene) (OPE) having comparable lengths and exhibits weaker length dependence. The conductance improvement in these diruthenium(II) molecules is ascribable to the better energy match of the Fermi level of gold electrodes with the HOMO that is mainly resident on the Ru–CC–CC–Ru backbone. Furthermore, modulation of molecular conductance is achieved by changing the length and π-conjugated system of the chelating 2,2′:6′,2′′-terpyridyl ligand.

Efficient photo-driven hydrogen evolution by binuclear nickel catalysts of different coordination in noble-metal-free systems.

Exploration of the complex Ni2(MBD)4 (MBD = 2-mercaptobenzimidazole) (C1) having different coordinated Ni atoms as a photocatalyst for hydrogen evolution is made. For comparison, the bimetallic Ni2(MBT)4 (MBT = 2-mercaptobenthiazole) (C2) complex with the same coordinated Ni atoms was synthesized. Both of the complexes have been successfully constructed for photo-induced hydrogen production using organic dyes as photosensitizers and triethanolamine (TEOA) as the effective electron donor by visible light (>400 nm) in acetonitrile-water solution. The time-dependence of H2 generation and DFT computational studies demonstrate that the complex C1 is more active than C2 for H2 evolution. The mechanisms of photocatalytic hydrogen generation for C1 and C2 involve different protonation sites resulting from the differences between the two structures.

Regulation of Charge Delocalization in a Heteronuclear Fe2Ru System by a Stepwise Photochromic Process

Heteronuclear complexes FeCp2 -DTE-C≡C-Ru(dppe)2 Cl (1u2009o; dppe=1,2-bis(diphenylphosphino)ethane, Cp=cyclopentadienyl, DTE=dithienylethene) and FeCp2-DTE-C≡C-Ru(dppe)2-C≡C-DTE-FeCp2 (2u2009oo), with redox-active ferrocenyl and ruthenium centers separated by a photochromic DTE moiety, were prepared to achieve photoswitchable charge delocalization and Fe⋅⋅⋅Ru electronic communication. Upon UV-light irradiation of 2u2009oo, the Fe⋅⋅⋅Ru heterometallic electronic interaction is increasingly facilitated with stepwise photocyclization, 2u2009oo→2u2009co→2u2009cc; this is ascribed to the gradual increase in π-conjugated systems. The near-infrared absorptions in mixed-valence species [2u2009oo](+) /[2u2009co](+) /[2u2009cc](+) are gradually intensified following the conversion of [2u2009oo](+) →[2u2009co](+) →[2u2009cc](+) , which demonstrates that the extent of charge delocalization shows progressive enhancement with stepwise photocyclization. As revealed by electrochemical, spectroscopic, and theoretical studies, complex 2 exhibits nine switchable states through stepwise photochromic and reversible redox processes.

Modulating Stepwise Photochromism in Platinum(II) Complexes with Dual Dithienylethene–Acetylides by a Progressive Red Shift of Ring-Closure Absorption

To modulate stepwise photochromism by shifting ring-closure absorption of the dithienylethene (DTE) moiety, trans-Pt(PEt3)2(C≡C-DTE)2 [C≡C-DTE = L1o (1oo), L2o (2oo), L3o (3oo), and L4o (4oo)] and cis-Pt(PEt3)2(L4o)2 (5oo) with two identical DTE-acetylides were elaborately designed. With the gradual red shift of ring-closure absorption for L1c (441 nm) → L2c (510 nm) → L3c (556 nm) → L4c (602 nm), stepwise photochromism is increasingly facilitated in trans-Pt(PEt3)2(C≡C-DTE)2 following 1oo → 2oo → 3oo → 4oo. The conversion percentage of singly ring-closed 2co-4co to dually ring-closed 2cc-4cc at the photostationary state is progressively increased in the order 1cc (0%) → 2cc (18%) → 3cc (67%) → 4cc (100%). Compared with trans-arranged 4oo, stepwise photochromism in the corresponding cis-counterpart 5oo is less pronounced, ascribed to either direct conversion of 5oo to 5cc or rapid conversion of 5co to 5cc. The progressively facile stepwise photocyclization following 2oo → 3oo → 4oo is reasonably interpreted by gradually enhanced transition character involving LUMO+1, which is the only unoccupied frontier orbital responsible for further photocyclization of singly ring-closed 2co-4co.

Solution-processed OLEDs based on phosphorescent PtAu2 complexes with phenothiazine-functionalized acetylides

Two triphosphine-participated PtAu2 heterotrinuclear complexes with phenothiazine functionalized acetylides were prepared. The crystal structural determination indicates that because of a short Pt–Au distance of 2.9549(4) A, the PtAu2 heterotrinuclear array supported by double triphosphine ligands exhibits substantial Pt–Au intermetallic contact. The PtAu2 complexes show moderate phosphorescent emission in fluid solution and the powder state, but intense orange and yellow phosphorescence in doped poly(methyl methacrylate) films with quantum yields of 73.7% and 48.9%, respectively. The phosphorescence arises from an admixture of 3[π(phenothiazine–acetylide) → π*(triphosphine)] 3LLCT and 3[π(phenothiazine–acetylide) → p/s(PtAu2)] 3LMCT triplet excited states. Utilizing blended host materials composed of both hole-transport TAPC and electron-transport OXD-7 doping with 8% phosphorescent PtAu2 complex as emitting layer, solution-processed organic light-emitting diodes (OLEDs) gave orange electroluminescence with the highest current efficiency of 35.4 cd A−1 and external quantum efficiency of 18.7%.

Multistate and Multicolor Photochromism through Selective Cycloreversion in Asymmetric Platinum(II) Complexes with Two Different Dithienylethene-Acetylides.

Four asymmetric bis(dithienylethene-acetylide) platinum(II) complexes trans-Pt(PEt3)2(L1o)(L5o) (1oo), trans-Pt(PEt3)2(L2o)(L5o) (2oo), trans-Pt(PEt3)2(L3o)(L5o) (3oo), and trans-Pt(PEt3)2(L4o)(L5o) (4oo) with two different dithienylethene-acetylides (L1o-L5o) were designed to modulate stepwise, multistate, and multicolor photochromism by modifying ring-closure absorption wavelengths. Upon irradiation under UV light, 1oo converts only to 1oc without the observation of 1co and dually ring-closed species 1cc. In contrast, both mixed ring-open/closed species oc and co as well as dually ring-closed species cc are observed upon UV light irradiation of 2oo-4oo, implying that a substantial stepwise photochromic process occurs following 2oo-4oo → 2oc-4oc/2co-4co → 2cc-4cc. The conversion percentage of dually ring-closed species at the photostationary state (PSS) is progressively increased following 1cc (0%) → 2cc (40%) → 3cc (86%) → 4cc (>95%), coinciding with the progressive red-shift of ring-closure absorption bands in free L1c (441 nm) → L2c (510 nm) → L3c (556 nm) → L4c (591 nm). Particularly, compound 2 affords four states (2oo, 2co, 2oc, and 2cc) with different colors (colorless, purple, blue, and dark blue, respectively) through a selective photochemical cycloreversion process upon irradiation with appropriate wavelengths of light. Although stepwise photocyclization reactions 3oo → 3co/3oc → 3cc and 4oo → 4co/4oc → 4cc are observed, multicolor photochromism of 3oo and 4oo could not be achieved because ring-closure absorption bands between L3c/L4c and L5c are significantly overlapped. The stepwise photochemical processes are well demonstrated by NMR, UV-vis, and infrared (IR) spectroscopy and time-dependent density functional theory (TD-DFT) computational studies.

Photoswitchable electrochemical behaviour of a [FeFe] hydrogenase model with a dithienylethene derivative

A diiron dithiolate complex 1o with a dithienylethene (DTE) phosphine ligand has been elaborately designed and fully investigated by spectroscopic and DFT computational studies. Upon irradiation with UV light, the DTE moiety in complex 1o undergoes an excellent photocyclization reaction to attain ring-closed state 1c in high yield (>95%), accompanied by a colour change from orange to deep blue. On the other hand, upon irradiation with visible light (>460 nm), ring-closed form 1c in CH(3)CN solution reverts perfectly into ring-open form 1o. Both 1o and 1c were characterised by IR, (1)H, (31)P, (19)F NMR and electrochemical spectroscopy. The electrochemical behaviours of both the open and closed forms were investigated by cyclic voltammetry. Upon photocyclization reaction, a 290 mV (from -2.29 V to -2.00 V) positive shift is induced in the potential of electrochemical catalytic proton reduction, due to the electron-withdrawing effect of the ring-closed DTE moiety. Consequently, complex 1 can reversibly photoswitch the potential of proton reduction on the [FeFe] moiety.