Dinuclear and Trinuclear Nickel Complexes as Effective Catalysts for Alternating Copolymerization on Carbon Dioxide and Cyclohexene Oxide.

A series of novel nickel complexes 1-9 supported by NNO-tridentate Schiff-base derivatives have been synthesized and characterized. Treatment of the pro-ligands [L(1)-H = 2,4-di-tert-butyl-6-(((2-(dimethylamino)ethyl)imino)methyl)phenol, L(2)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-4,6-bis(2-phenylpropan-2-yl)phenol, L(3)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)phenol] with Ni(OAc)2·4H2O in refluxing ethanol afforded mono- or bimetallic nickel complexes {[(L(1))Ni(OAc)] (1); (L(2))Ni(OAc)] (2); (L(3))2Ni2(OAc)2(H2O)] (3)}. Alcohol-solvated trimetallic nickel acetate complexes {[(L(3))2Ni3(OAc)4(MeOH)2] (4); (L(3))2Ni3(OAc)4(EtOH)2] (5)} could be generated from the reaction of L(3)-H and anhydrous nickel(II) acetate with a ratio of 2:3 in refluxing anhydrous MeOH or EtOH. The reaction of nickel acetate tetrahydrate and L(4)-H to L(6)-H [L(4)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-5-methoxyphenol, L(5)-H = 2-(((2-(dimethylamino)ethyl)imino)methyl)-4-methoxy-phenol, L(6)-H = 2-(((2-(dimethylamino)ethyl)imino)(phenyl)methyl)phenol] produced, respectively, the alcohol-free trinuclear nickel complexes {[(L(4))2Ni3(OAc)4] (7); [(L(5))2Ni3(OAc)4] (8); [(L(6))2Ni3(OAc)4] (9)} with the same ratio in refluxing EtOH under the atmospheric environment. Interestingly, recrystallization of [(L(3))2Ni3(OAc)4(MeOH)] (4) or [(L(3))2Ni3(OAc)4(EtOH)] (5) in the mixed solvent of CH2Cl2/hexane gives [(L(3))2Ni3(OAc)4] (6), which is isostructural with analogues 7-9. All bi- and trimetallic nickel complexes exhibit efficient activity and good selectivity for copolymerization of CO2 with cyclohexene oxide, resulting in copolymers with a high alternating microstructure possessing ≥99% carbonate-linkage content. This is the first example to apply well-defined trinuclear nickel complexes as efficient catalysts for the production of perfectly alternating poly(cyclohexene carbonate).

Synthesis and Characterization of Novel Triarylamine Derivatives with Dimethylamino Substituents for Application in Optoelectronic Devices.

Two novel triphenylamine-based derivatives with dimethylamino substituents, N, N'-bis(4-dimethylaminophenyl)- N, N'-bis(4-methoxyphenyl)-1,4-phenylenediamine (NTPPA) and N, N'-bis(4-dimethylaminophenyl)- N, N'-bis(4-methoxyphenyl)-1,1'-biphenyl-4,4'-diamine (NTPB), were readily prepared for investigating the optical and electrochromic behaviors. These two obtained materials were introduced into electrochromic devices accompanied with heptyl viologen (HV), and the devices demonstrate a high average coloration efficiency of 287 cm2/C and electrochemical stability. Besides, NTPB/HV was further used to fabricate electrofluorochromic devices with a gel type electrolyte, and exhibit a controllable and high photoluminescence contrast ratio ( Ioff/ Ion) of 32.12 from strong emission to truly dark by tuning the applied potential in addition to a short switching time of 4.9 s and high reversibility of 99% after 500 cycles.

A novel panchromatic shutter based on an ambipolar electrochromic system without supporting electrolyte.

Two triphenylamine derivatives, N,N,N',N'-tetrakis(4-methoxyphenyl)-1,4-phenylenediamine TPPA and N,N,N',N'-tetrakis(4-methoxyphenyl)-1,1'-biphenyl-4,4'-diamine TPB, were successfully prepared and combined with HV to fabricate the electrochromic device as a panchromatic shutter for the application of transparent display. The obtained electrochromic device exhibits exceptional novel electrochromic properties, including enhanced color contrast, switching time, and long-term stability. Furthermore, it is worth mentioning that the most important contribution of this ambipolar system approach is that no supporting electrolyte is added into the device.