Narrowband room temperature phosphorescence of closed-loop molecules through the multiple resonance effect.

Luminescent materials with narrowband emission show great potential for diverse applications in optoelectronics. Purely organic phosphors with room-temperature phosphorescence (RTP) have made significant success in rationally manipulating quantum efficiency, lifetimes, and colour gamut in the past years, but there is limited attention on the purity of the RTP colours. Herein we report a series of closed-loop molecules with narrowband phosphorescence by multiple resonance effect, which significantly improves the colour purity of RTP. Phosphors show narrowband phosphorescence with full width at half maxima (FWHM) of 30 nm after doping into a rigid benzophenone matrix under ambient conditions, of which the RTP efficiency reaches 51.8%. At 77 K, the FWHM of phosphorescence is only 11 nm. Meanwhile, the colour of narrowband RTP can be tuned from sky blue to green with the modification of methyl groups. Additionally, the potential applications in X-ray imaging and display are demonstrated. This work not only outlines a design principle for developing narrowband RTP materials but also makes a major step forward extending the potential applications of narrowband luminescent materials in optoelectronics.

Achieving High-Temperature Phosphorescence by Organic Cocrystal Engineering.

Organic phosphors offer a promising alternative in optoelectronics, but their temperature-sensitive feature has restricted their applications in high-temperature scenarios, and the attainment of high-temperature phosphorescence (HTP) is still challenging. Herein, a series of organic cocrystal phosphors are constructed by supramolecular assembly with an ultralong emission lifetime of up to 2.16 s. Intriguingly, remarkable stabilization of triplet excitons can also be realized at elevated temperature, and green phosphorescence is still exhibited in solid state even up to 150 °C. From special molecular packing within the crystal lattice, it has been observed that the orientation of isolated water cluster and well-controlled molecular organization via multiple interactions can favor the structural rigidity of cocrystals more effectively to suppress the nonradiative transition, thus resulting in efficient room-temperature phosphorescence and unprecedented survival of HTP.

Seeded-growth self-assembled polymerization of a ferrocene-bearing palladium(II)-terpyridyl bimetallic complex.

A new bimetallic complex containing a 4'-ferrocenyl-(2,2':6',2''-terpyridine)palladium core with polyethylene glycol-based pyridine is applied in seeded-growth self-assembled supramolecular polymerization, which affords nanoribbons with controllable lengths and the process follows a first-order reaction kinetics. This approach is successfully demonstrated for a bimetallic organic complex for the first time.

Photo-thermo-induced room-temperature phosphorescence through solid-state molecular motion.

The development of smart-responsive materials, in particular those with non-invasive, rapid responsive phosphorescence, is highly desirable but has rarely been described. Herein, we designed and prepared a series of molecular rotors containing a triazine core and three bromobiphenyl units: o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ. The bromine and triazine moieties serve as room temperature phosphorescence-active units, and the bromobiphenyl units serve as rotors to drive intramolecular rotation. When irradiated with strong ultraviolet photoirradiation, intramolecular rotations of o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ increase, successively resulting in a photothermal effect via molecular motions. Impressively, the photothermal temperature attained by p-Br-TRZ is as high as 102 °C, and synchronously triggers its phosphorescence due to the ordered molecular arrangement after molecular motion. The thermal effect is expected to be important for triggering efficient phosphorescence, and the photon input for providing a precise and non-invasive stimulus. Such sequential photo-thermo-phosphorescence conversion is anticipated to unlock a new stimulus-responsive phosphorescence material without chemicals invasion.

Nanoimprint Lithography-Directed Self-Assembly of Bimetallic Iron-M (M=Palladium, Platinum) Complexes for Magnetic Patterning.

Self-assembly of d8 metal polypyridine systems is a well-established approach for the creation of 1D organometallic assemblies but there are still challenges for the large-scale construction of nanostructured patterns from these building blocks. We describe herein the use of high-throughput nanoimprint lithography (NIL) to direct the self-assembly of the bimetallic complexes [4'-ferrocenyl-(2,2':6',2''-terpyridine)M(OAc)]+ (OAc)- (M=Pd or Pt; OAc=acetate). Uniform nanorods are fabricated from the molecular self-organization and evidenced by morphological characterization. More importantly, when top-down NIL is coupled with the bottom-up self-assembly of the organometallic building blocks, regular arrays of nanorods can be accessed and the patterns can be controlled by changing the lithographic stamp, where the mold imposes a confinement effect on the nanorod growth. In addition, patterns consisting of the products formed after pyrolysis are studied. The resulting arrays of ferromagnetic FeM alloy nanorods suggest promising potential for the scalable production of ordered magnetic arrays and fabrication of magnetic bit-patterned media.

A Tetrakis(terpyridine) Ligand-Based Cobalt(II) Complex Nanosheet as a Stable Dual-Ion Battery Cathode Material.

Inspired by the flexibility of the bottom-up approach in terms of selecting molecular components and thus tailoring functionalities, a terpyridine derivative (1,2,4,5-tetrakis(4-(2,2':6',2″-terpyridyl)phenyl)benzene) (Tetra-tpy) is synthesized and coordinated with Co(II) ion to self-assemble into a nanosheet Co-sheet by a facile interface-assisted synthesis. The bis(terpyridine)-Co(II) complex nanosheet formed not only shows good stability, but also features the layered structure and rich electrochemical activity inherited from the embedded Co(terpyridine)2 motif. Thus, Co-sheet can serve as a cathode material for a dual-ion battery prototype, which exhibits a high utilization of redox-active sites, good cycling stability, and rate capability, thus expanding the potential application of this kind of easily prepared metal-complex nanosheets in the field of energy storage.

Complex assembly from planar and twisted π-conjugated molecules towards alloy helices and core-shell structures.

Integrating together two dissimilar π-conjugated molecules into controlled complex topological configurations remains a largely unsolved problem owing to the diversity of organic species and their respective different assembly features. Here, we find that two structurally similar organic semiconductors, 9,10-bis(phenylethynyl)anthracene (BA) and 5,12-bis(phenylethynyl)naphthacene (BN), co-assemble into two-component helices by control of the growth kinetics as well as the molar ratio of BA/BN. The helical superstructures made of planar and twisted bis(phenylethynyl) derivatives can be regarded as (BA)x(BN)1-x alloys, which are formed due to compatible structural relationship between BA and BN. Moreover, epitaxial growth of (BA)x(BN)1-x alloy layer on the surface of BA tube to form BA@(BA)x(BN)1-x core-shell structure is also achieved via a solute exchange process. The precise control over composition and morphology towards organic alloy helices and core-shell microstructures opens a door for understanding the complex co-assembly features of two or more different material partners with similar structures.

A molecular approach to magnetic metallic nanostructures from metallopolymer precursors.

In recent years, metallopolymers have attracted much attention as precursors to generate magnetic metal/metal alloy nanoparticles (NPs) through pyrolysis or photolysis because they offer the advantages of ease of solution processability, atomic level mixing and stoichiometric control over composition. The as-generated NPs usually possess narrow size distributions with precise control of composition and density per unit area. Moreover, patterned NPs can be achieved on various substrates in this way owing to the good film-forming property of metallopolymers and such work is important for many applications based on metal nanostructures. By combining the merits of both the solution processability of metallopolymers and nanoimprint lithography (NIL), a new platform can be created for fabricating bit-patterned media (BPM) and the next-generation of nanoscale ultra-high-density magnetic data storage devices. Furthermore, most of these metallopolymers can be used directly as a negative-tone resist to generate magnetic metallic nanostructures by electron-beam lithography and UV photolithography. Self-assembly and subsequent pyrolysis of metalloblock copolymers can also afford well-patterned magnetic metal or metal alloy NPs in situ with periodicity down to dozens of nanometers. In this review, we highlight the use of metallopolymer precursors for the synthesis of magnetic metal/metal alloy NPs and their nanostructures and the related applications.

Patterning of L10 FePt nanoparticles with ultra-high coercivity for bit-patterned media.

L10-ordered FePt nanoparticles (NPs) with ultra-high coercivity were directly prepared from a new metallopolyyne using a one-step pyrolysis method. The chemical ordering, morphology and magnetic properties of the as-synthesized FePt NPs have been studied. Magnetic measurements show the coercivity of these FePt NPs is as high as 3.6 T. Comparison of NPs synthesized under the Ar and Ar/H2 atmospheres shows that the presence of H2 in the annealing environment influences the nucleation and promotes the growth of L10-FePt NPs. Application of this metallopolymer for bit-patterned media was also demonstrated using nanoimprint lithography.

Additive and Photochemical Manufacturing of Copper.

In recent years, 3D printing technologies have been extensively developed, enabling rapid prototyping from a conceptual design to an actual product. However, additive manufacturing of metals in the existing technologies is still cost-intensive and time-consuming. Herein a novel platform for low-cost additive manufacturing is introduced by simultaneously combining the laser-induced forward transfer (LIFT) method with photochemical reaction. Using acrylonitrile butadiene styrene (ABS) polymer as the sacrificial layer, sufficient ejection momentum can be generated in the LIFT method. A low-cost continuous wave (CW) laser diode at 405 nm was utilized and proved to be able to transfer the photochemically synthesized copper onto the target substrate. The wavelength-dependent photochemical behaviour in the LIFT method was verified and characterized by both theoretical and experimental studies compared to 1064 nm fiber laser. The conductivity of the synthesized copper patterns could be enhanced using post electroless plating while retaining the designed pattern shapes. Prototypes of electronic circuits were accordingly built and demonstrated for powering up LEDs. Apart from pristine PDMS materials with low surface energies, the proposed method can simultaneously perform laser-induced forward transfer and photochemical synthesis of metals, starting from their metal oxide forms, onto various target substrates such as polyimide, glass and thermoplastics.

Photochemical Copper Coating on 3D Printed Thermoplastics.

3D printing using thermoplastics has become very popular in recent years, however, it is challenging to provide a metal coating on 3D objects without using specialized and expensive tools. Herein, a novel acrylic paint containing malachite for coating on 3D printed objects is introduced, which can be transformed to copper via one-step laser treatment. The malachite containing pigment can be used as a commercial acrylic paint, which can be brushed onto 3D printed objects. The material properties and photochemical transformation processes have been comprehensively studied. The underlying physics of the photochemical synthesis of copper was characterized using density functional theory calculations. After laser treatment, the surface coating of the 3D printed objects was transformed to copper, which was experimentally characterized by XRD. 3D printed prototypes, including model of the Statue of Liberty covered with a copper surface coating and a robotic hand with copper interconnections, are demonstrated using this painting method. This composite material can provide a novel solution for coating metals on 3D printed objects. The photochemical reduction analysis indicates that the copper rust in malachite form can be remotely and photo-chemically reduced to pure copper with sufficient photon energy.

Metallopolymer precursors to L10-CoPt nanoparticles: synthesis, characterization, nanopatterning and potential application.

Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium.

Effect of butterfly-shaped sulfur-bridged ligand and counter anions on the catalytic activity and diastereoselectivity of organobismuth complexes.

In the direct Mannich reaction and synthesis of α,ß-unsaturated ketones, the use of organobismuth complexes as catalysts leads to high diastereoselectivity and products of single trans conformation. In this paper, we illustrate the relationship between structure and catalytic activity as well as diastereoselectivity of organobismuth complexes having a 5,6,7,12-tetrahydrodibenz [c,f][1,5]thiobismocine framework as well as bearing a butterfly-shaped sulfur-bridged ligand and tunable anions. With the exposed bismuth center acting as a Lewis acid site and the uncoordinated lone pair electrons of sulfur as a Lewis base site, the cationic organobismuth complexes work as bifunctional Lewis acid/base catalysts. Due to the steric influence of the butterfly-shaped structure and synergistic effect of Lewis acid and Lewis base centers, the complexes can direct substrate attack in organic synthesis. By adjusting the electron-withdrawing ability of the counter anions, the S-Bi bond strength can be regulated, leading to a significant change in Lewis acidity and Lewis basicity as well as catalytic activity. Through synergistic modulation of the above effects, one can control the diastereoselectivity of the organobismuth complexes for the generation of a single diastereoisomer.