A-LLTO Nanoparticles Embedded Composite Solid Polymer Electrolyte for Room Temperature Operational Li-metal Batteries.

Solid-state batteries (SSBs) have the potential to revolutionize the current energy storage sector. A significant portion of the current development of electric vehicles and the electrification of various appliances relies on Lithium (Li)-ion batteries. However, future energy demands will require the development of stronger and more reliable batteries. This report presents a novel solid state electrolyte (SSE) composed of a self-healing composite solid polymer electrolyte (CSPE) matrix and aluminum-doped (Li0.33La0.56)1.005Ti0.99Al0.01O3 (A-LLTO) nanofillers. The CSPE contains Jeffamine ED-2003 monomer, Benzene-1,3,5-tricarbaldehyde (BTC) crosslinker dissolved in a 1:1 ratio of Dimethylformamide (DMF) to LiPF6, and a certain amount (x) of A-LLTO nanofillers (x = 5, 7.5, 10, 12.5%). A CSPE containing x-amount of A-LLTO fillers (referred to as CAL-x%) demonstrates excellent ion-conducting properties and stable battery performance. The CAL-10% demonstrates 1.1 × 10-3 S cm-1 of ionic conductivity at room temperature (RT). A-LLTO nanofillers dispersed uniformly within the polymer matrix form a percolation network, which is believed to improve ionic conductivity and the diffusion of Li+ ions. The CR-2032 cell, consisting of LiFePO4 (LFP)║CAL-10%║Li, at RT offers an initial discharge capacity of ≈165 mAh g-1 at 0.1C rate for 120 cycles with 98.85% coulombic efficiency (C.E.).

Interfacial Layer Materials with a Truxene Core for Dopant-Free NiOx -Based Inverted Perovskite Solar Cells.

Nickel oxide (NiOx ) is commonly used as a holetransporting material (HTM) in p-i-n perovskite solar cells. However, the weak chemical interaction between the NiOx and CH3 NH3 PbI3 (MAPbI3 ) interface results in poor crystallinity, ineffective hole extraction, and enhanced carrier recombination, which are the leading causes for the limited stability and power conversion efficiency (PCE). Herein, two HTMs, TRUX-D1 (N2 ,N7 ,N12 -tris(9,9-dimethyl-9H-fluoren-2-yl)-5,5,10,10,15,15-hexaheptyl-N2 ,N7 ,N12 -tris(4-methoxyphenyl)-10,15-dihydro-5H-diindeno[1,2-a:1',2'-c]fluorene-2,7,12-triamine) and TRUX-D2 (5,5,10,10,15,15-hexaheptyl-N2 ,N7 ,N12 -tris(4-methoxyphenyl)-N2 ,N7 ,N12 -tris(10-methyl-10H-phenothiazin-3-yl)-10,15-dihydro-5H-diindeno[1,2-a:1',2'-c]fluorene-2,7,12-triamine), are designed with a rigid planar C3 symmetry truxene core integrated with electron-donating amino groups at peripheral positions. The TRUX-D molecules are employed as effective interfacial layer (IFL) materials between the NiOx and MAPbI3 interface. The incorporation of truxene-based IFLs improves the quality of perovskite crystallinity, minimizes nonradiative recombination, and accelerates charge extraction which has been confirmed by various characterization techniques. As a result, the TRUX-D1 exhibits a maximum PCE of up to 20.8% with an impressive long-term stability. The unencapsulated device retains 98% of their initial performance following 210 days of aging in a glove box and 75.5% for the device after 80 days under ambient air condition with humidity over 40% at 25 °C.

Steric Effects on the Photovoltaic Performance of Panchromatic Ruthenium Sensitizers for Dye-Sensitized Solar Cells.

Three new heteroleptic Ru complexes, CYC-B22, CYC-B23C, and CYC-B23T, were prepared as sensitizers for coadsorbent-free, panchromatic, and efficient dye-sensitized solar cells. They are simultaneously functionalized with highly conjugated anchoring and ancillary ligands to explore the electronic and steric effects on their photovoltaic characteristics. The coadsorbent-free device based on CYC-B22 achieved the best power conversion efficiency (PCE) of 8.63% and a panchromatic response extending to 850 nm. The two stereoisomers, CYC-B23C and CYC-B23T coordinated with an unsymmetrical anchoring ligand, display similar absorption properties and the same driving forces for electron injection as well as dye regeneration. Nevertheless, the devices show not only the remarkably distinct PCE (6.64% vs 8.38%) but also discernible stability. The molecular simulation for the two stereoisomers adsorbed on TiO2 clarifies the distinguishable distances (16.9 Å vs 19.0 Å) between the sulfur atoms in the NCS ligands and the surface of the TiO2, dominating the charge recombination dynamics and iodine binding and therefore the PCE and stability of the devices. This study on the steric effects caused by the highly conjugated and unsymmetrical anchoring ligand on the adsorption geometry and photovoltaic performance of the dyes paves a new way for advancing the molecular design of polypyridyl metal complex sensitizers.

Recent Progress of Helicene Type Hole-Transporting Materials for Perovskite Solar Cells.

Perovskite solar cells have emerged as one of the most promising photovoltaic technologies for future clean energy sources to replace fossil fuels. Among the various components in a perovskite solar cell, the hole-transporting materials play significant roles in boosting device performance and stability. Recently, hole-transporting materials with helicene cores have received much attention due to their unique properties and ability to improve the performance and stability of the perovskite solar cells. The focus of this review is on the emerging special class of HTMs based on helicenes for perovskite solar cells. The optical, electrochemical, thermal and photovoltaic properties of helicene-based small molecules as HTMs or interfacial layer materials in n-i-p or p-i-n type perovskite solar cells are summarized. Finally, perspectives for the future development of helicene type hole-transporting materials are provided.

Solvatochromic Fluorescence of a GFP Chromophore-Containing Organogelator in Solutions and Organogels.

Solvatofluorochromism, a solvation effect on the fluorescence color of an organic dye, is a property generally limited to fluid solutions. We demonstrate herein the concept of solid-state solvatofluorochromism by using an organogelator (1-SG), which consists of a solvatofluorochromic green fluorescence protein (GFP) chromophore (1) and a sugar gelator (SG). While 1-SG could be located in the liquid phase or in the fibrous solid matrix of the SG gel, our results show that the one in the solid matrix but near the liquid interface has superior fluorescence stability and quantum efficiency as well as solvatofluorochromicity than the one in the liquid phase. In addition, the phenomenon of fluorescence turn-on occurs when the gel is formed in protic solvents. These features have been applied to perform multicolor fluorescence patterning, chemical vapor sensing, data encryption and decryption, and real-time fluorescence cell imaging.

Tailoring Photophysical Properties of Diketopyrrolopyrrole Small Molecules with Electron-Withdrawing Moieties for Efficient Solar Steam Generation.

The development of photothermal materials (PTMs) for solar steam generation (SSG) has gained tremendous attention in response to the global clean water scarcity issue. However, the investigation in employing organic small-molecule PTMs for SSG applications is rarely found due to their narrow optical absorption range to harvest solar energy and insufficient photostability for long-term use. Herein, we employ a diketopyrrolopyrrole (DPP) core unit together with electron-withdrawing (EW) endcaps and siloxane side chains to introduce stronger intramolecular charge transfer (ICT) characteristics as well as the hydrophobic character. The enhanced ICT characteristics of DPP derivatives render a broad optical absorption range, less emission, and a high nonradiative decay rate for efficient solar energy harvesting and photothermal effects. Meanwhile, the hydrophobic nature of these DPP derivatives allows the facile fabrication of novel Janus photothermal membranes for effective water vaporization and solar-to-vapor conversion efficiency. By embedding DPP derivatives to the SSG device, we showed that the solar-to-vapor efficiency can reach up to 71.8% under relatively low visible light power (∼700 W m-2), which is, on average, 2.66 times higher than that of bulk water of similar dimension. Moreover, this report demonstrates the great potential of conjugated small molecules for photothermal applications, owing to their versatility and flexibility in structural engineering and its diminishing radiative decay properties. This may inspire more innovation and advancement in SSG applications.

Structural Engineering of Organic D-A-π-A Dyes Incorporated with a Dibutyl-Fluorene Moiety for High-Performance Dye-Sensitized Solar Cells.

Structural engineering of the light-harvesting dyes employed in DSSCs (dye-sensitized solar cells) with a systematic choice of the electron-donating and -accepting groups as well as the π-bridge allows the (photo)physical properties of dyes to match the criteria needed for improving the DSSC efficiency. Herein, we report an effective approach of molecular engineering of DSSC sensitizers, aiming to gain insights on the configurational impact of the fluorenyl unit on the optoelectronic properties and photovoltaic performance of DSSCs. Five new organic dyes (GZ116, GZ126, GZ129, MA1116, and MA1118) with a D-A-π-A framework integrated with a fluorenyl moiety were designed and synthesized for DSSCs. The fluorenyl unit is configured as part of the π-spacer for the GZ series, whereas it connected on the electron-deficient quinoxaline motif for the MA series. The devices fabricated from the MA1116 sensitizer produced the best performance under standard AM 1.5 G solar conditions as well as dim-light (300-6000 lx) illumination. The devices fabricated from MA1116 displayed a PCE of 8.68% (Jsc = 15.00 mA cm-2, Voc = 0.82 V, and FF = 0.71) under 1 sun and 26.81% (Jsc = 0.93 mA cm-2, Voc = 0.68 V, and FF = 0.76) under 6000 lx illumination. The device efficiency based on dye MA1116 under 1 sun outperformed that based on the standard N719 dye, whereas a comparable performance between devices based on MA1116 and N719 was achieved under dim-light conditions. A combination of enhancing the charge separation, suppressing dye aggregation, and providing better insulation that prevents the oxidized redox mediator from approaching the TiO2 surface all contribute to the superior performance of DSSCs fabricated based on these light-harvesting dyes. The judicious integration of the fluorenyl unit in a D-A-π-A-based DSSC would be a promising strategy to boost the device performance.

Low-Cost Hole-Transporting Materials Based on Carbohelicene for High-Performance Perovskite Solar Cells.

Two hole-transporting materials (HTMs) based on carbohelicene cores, CH1 and CH2, are developed and used in fabricating efficient and stable perovskite solar cells (PSCs). Owing to the rigid conformation of the helicene core, both compounds possess unique CH-π interactions in the crystalline packing pattern and good phase stability, which are distinct from the π-π intermolecular interactions of conventional planar and spiro-type molecules. PSCs based on CH1 and CH2 as HTMs deliver excellent device efficiencies of 19.36 and 18.71%, respectively, outperforming the control device fabricated with spiro-OMeTAD (18.45%). Furthermore, both PSCs exhibit better ambient stability, with 90% of initial performance retained after aging with a 50-60% relative humidity at 25 °C for 500 h. Due to the low production cost of both compounds, these newly designed carbohelicene-type HTMs have the potential for the future commercialization of PSCs.

Heptacene: Synthesis and Its Hole-Transfer Property in Stable Thin Films.

Heptacene (1) has been produced via a monoketone precursor, 2, which was prepared from 1,2,4,5-tetrabromobenzene in nine steps in a total yield of 10 %. Compound 2 was converted to 1 quantitatively by heating at 202 °C. Heptacene exhibited high thermal stability in the solid state without any observable change over two months. To investigate the potential value of 1 as a material for p-type organic field-effect transistors (OFETs), top-contact OFET devices were fabricated by vacuum deposition of 1 onto a hexamethyldisilazane (HMDS)/SiO2 /Si substrate. The best hole mobility performance was 2.2 cm2  V-1 s-1 . This is the first report of stable heptacene being used in an effective device and examined for its charge carrier properties.

Hydrogen Bonding-Induced H-Aggregation for Fluorescence Turn-On of the GFP Chromophore: Supramolecular Structural Rigidity.

To turn on the fluorescence of the native green fluorescence protein (GFP) chromophore, 4-hydroxybenzylidene-dimethylimidazolinone (HBDI), in an artificial supramolecular system has been a challenging task, because it requires high local environmental rigidity. This work shows that the formation of H-aggregates of an HBDI-containing organogelator results in two orders of magnitude fluorescence enhancement (Φf =2.9 vs. 0.02 %), in which the inter-HBDI OH⋅⋅⋅OH H-bonds play a crucial role. The aggregation-induced fluorescence enhancement of HBDI has important implications on the origin of the high fluorescence quantum efficiency of HBDI in the GFP ß-barrel and on the supramolecular strategy for a full fluorescence recovery of HBDI. These results reveal a new approach to designing rigid chromophore aggregates for high-performance optoelectronic properties.

Synthesis, Luminescence, and Structure of a Polymorphic Polyfluorinated Diiodoplatinum(II) Diimine Complex.

PtI2(5,5'-bis(HCF2CH2OCH2)-2,2'-bpy)], 55-2FH-PtI2, is the first example of a substituted fluorinated diiodoplatinum diimine complex that exhibits polymorphism. The complex, upon recrystallization, forms two different polymorphs, denoted as α and ß forms. The luminescence of the α and ß forms are the same in glassy solution at 77 K; however, in the solid state, they differ significantly. The major difference between them lies in the solid-state packing of the crystalline structure. The α form is a square planar polyfluorinated PtI2-containing complex. Its extended herringbone structure consists of two neighboring stacked bipyridyl planes that do not overlap. The α form emits stronger than its parent molecule, [PtI2bpy], and much stronger than the ß polymorph. The ß form has a slight tetrahedral distortion about the metal center that ultimately changes the geometry of the complex and decreases the d-orbital splitting from square planar. Furthermore, overlapping bipyridine rings in the extended structure of the ß form quench the emission thus resulting in a lower energy emission. Additionally, the ß form shows only one type of C-H···O intermolecular stacking interaction that can cause the moderate distortion of the metal core.

Lipid-Wrapped Upconversion Nanoconstruct/Photosensitizer Complex for Near-Infrared Light-Mediated Photodynamic Therapy.

Photodynamic therapy (PDT) is a noninvasive medical technology that has been applied in cancer treatment where it is accessible by direct or endoscope-assisted light irradiation. To lower phototoxicity and increase tissue penetration depth of light, great effort has been focused on developing new sensitizers that can utilize red or near-infrared (NIR) light for the past decades. Lanthanide-doped upconversion nanoparticles (UCNPs) have a unique property to transduce NIR excitation light to UV-vis emission efficiently. This property allows some low-cost, low-toxicity, commercially available visible light sensitizers, which originally are not suitable for deep tissue PDT, to be activated by NIR light and have been reported extensively in the past few years. However, some issues still remain in the UCNP-assisted PDT platform such as colloidal stability, photosensitizer loading efficiency, and accessibility for targeting ligand installation, despite some advances in this direction. In this study, we designed a facile phospholipid-coated UCNP method to generate a highly colloidally stable nanoplatform that can effectively load a series of visible light sensitizers in the lipid layers. The loading stability and singlet oxygen generation efficiency of this sensitizer-loaded lipid-coated UCNP platform were investigated. We also have demonstrated the enhanced cellular uptake efficiency and tumor cell selectivity of this lipid-coated UCNP platform by changing the lipid dopant. On the basis of the evidence of our results, the lipid-complexed UCNP nanoparticles could serve as an effective photosensitizer carrier for NIR light-mediated PDT.

New Helicene-Type Hole-Transporting Molecules for High-Performance and Durable Perovskite Solar Cells.

Three azahelicene derivatives with electron-rich bis(4-methoxyphenyl)amino or bis( p-methoxyphenyl)aminophenyl groups at the terminals were deliberately designed, synthesized, and characterized as hole-transporting materials (HTMs) for perovskite solar cells (PSCs). Optical and thermal properties, energy level alignments, film morphologies, hole extraction ability, and hole mobility were studied in detail. PSCs using the newly synthesized molecules as HTMs were fabricated. A maximum power conversion efficiency (PCE) of 17.34% was observed for the bis( p-methoxyphenyl)amino-substituted derivative (SY1) and 16.10% for the bis( p-methoxyphenyl)aminophenyl-substituted derivative (SY2). Longer-chain substituent such as hexyloxy group greatly diminishes the efficiency. In addition, the dopant-free devices fabricated with SY1 as the HTM shows an average PCE of 12.13%, which is significantly higher than that of spiro-OMeTAD (7.61%). The ambient long-term stability test revealed that after 500 h, the devices prepared from SY1 and SY2 retained more than 96% of its initial performance, which is much improved than the reference device with standard spiro-OMeTAD as the HTM under the same conditions. Detailed material cost analysis reveals that the material cost for SY1 is less than 8% of that for spiro-OMeTAD. These results provide a useful direction for designing a new class of HTMs to prepare highly efficient and more durable PSCs.

Synthesis and physical properties of brominated hexacene and hole-transfer properties of thin-film transistors.

A halide-substituted higher acene, 2-bromohexacene, and its precursor with a carbonyl bridge moiety were synthesized. The precursor was synthesized through 7 steps in a total yield of 2.5%. The structure of precursor and thermally converted 2-bromohexacene were characterized by solid state NMR, IR, and absorption spectra, as well as by DFT computation analysis. It exhibited high stability in the solid state over 3 months, therefore can be utilized in the fabrication of opto-electronic devices. The organic thin-film transistors (OFETs) were fabricated by using 2-bromohexacene and parent hexacene through vaccum deposition method. The best film mobility of 2-bromohexacene was observed at 0.83 cm2 V-1 s-1 with an on/off ratio of 5.0 × 104 and a threshold of -52 V, while the best film mobility of hexacene was observed at 0.076 cm2 V-1 s-1 with an on/off ratio of 2.4 × 102 and a threshold of -21 V. AFM measurement of 2-bromohexacene showed smooth film formation. The averaged mobility of 2-bromohexacene is 8 fold higher than the non-substituted hexacene.

Fluorescence Enhancement of Unconstrained GFP Chromophore Analogues Based on the Push-Pull Substituent Effect.

Unlike the high fluorescence quantum yield of the naturally occurring green fluorescence protein (GFP, Φf ∼ 0.8), the GFP chromophore, a benzylidenedimethylimidazolinone (BDI) dye, is nearly nonfluorescent (Φf < 0.001) in common solutions at room temperature. While many efforts have been devoted into the BDI chromophore engineering for fluorescence recovery, limited success has been achieved for structurally unconstrained GFP chromophore analogues (uGFPc). Herein we report a rational design of uGFPc toward an unprecedentedly high fluorescence quantum efficiency of 0.60 in hexane. This is achieved by a combined ortho-CN and meta-dimethylamino substituent electronic effect that largely suppresses the Z → E photoisomerization (the τ torsion) reaction, which is the major nonradiative decay channel of uGFPc. The structural design relied on the assumptions that the τ torsion of the meta-amino-substituted BDI systems leads to a zwitterionic twisted intermediate state (1p*) and that destabilizing the 1p* state by an electron-withdrawing CN substituent at the ortho or para position could slow down the τ torsion. The observed CN position effect conforms to the design concept. The push-pull substitution of BDI also leads to sensitive fluorescence-quenching responses to electron donors such as trimethylamine and to H-bond donors such as methanol.

A General Strategy to Enhance the Performance of Dye-Sensitized Solar Cells by Incorporating a Light-Harvesting Dye with a Hydrophobic Polydiacetylene Electrolyte-Blocking Layer.

A unique strategy to suppress charge recombination effectively and enhance light harvesting in dye-sensitized solar cells (DSSCs) is demonstrated by the design of a new dipolar organic dye functionalized with a diacetylene unit, which is capable of undergoing a photoinduced crosslinking reaction to generate a hydrophobic polydiacetylene layer. The polydiacetylene layer serves as an electrolyte-blocking layer that effectively blocks the approach of the oxidized redox mediator and suppresses the dark current, and also plays a role in light harvesting owing to efficient energy transfer to the dipolar dyes. A 15 % efficiency improvement was achieved on going from the monomer dye (JSC =13.5 mA cm-2 , Voc =0.728 V, fill factor=0.73, η=7.17 %) to the crosslinked dye (JSC =14.9 mA cm-2 , Voc =0.750 V, fill factor=0.74, η=8.27 %) under AM 1.5 conditions.

Structural Tuning of Anion-Templated Motifs with External Stimuli through Crystal-to-Crystal Transformation.

Protonation of trans-1,2-bis(4-pyridyl)ethylene (4,4'-bpe) with dilute sulfuric acid (33 %) afforded a protonated adduct [{4,4'-bpe⋅2 H+ }2 {HSO4 }-2 {SO4 }-2 {H2 O}2 ] (1). The neighboring olefinic bond in 1 is in a suitable range (3.931-4.064 Å) to undergo a photochemical [2+2] cycloaddition reaction. Upon irradiation with UV light (365 nm), 1 undergoes a molecular sliding involving the 4,4'-bpe⋅2 H+ units, affording 2, stabilized through OSO4 ⋅⋅⋅π interactions. Heating 1 to 50° C leads to a 3D hydrogen-bonded organic framework (HOF) (3). This process occurs through thermal dissociation of the bisulfate anion. Diffusion of iodine through the crystal lattice of 1 and 3 enables the reduction of sulfate to bisulfate, affording a 1D hydrogen-bonded chain (4). Solid-state 13 C CPMAS NMR, IR, DSC, and powder XRD studies further support stimuli-responsive structural tuning through crystal-to-crystal transformation. All these conversions occur with significant translational and rotational movements along with a series of bond-breaking and bond-forming processes.

Cross-Linked Fluorescent Supramolecular Nanoparticles as Finite Tattoo Pigments with Controllable Intradermal Retention Times.

Tattooing has been utilized by the medical community for precisely demarcating anatomic landmarks. This practice is especially important for identifying biopsy sites of nonmelanoma skin cancer (NMSC) due to the long interval (i.e., up to 3 months) between the initial diagnostic biopsy and surgical treatment. Commercially available tattoo pigments possess several issues, which include causing poor cosmesis, being mistaken for a melanocytic lesion, requiring additional removal procedures when no longer desired, and potentially inducing inflammatory responses. The ideal tattoo pigment for labeling of skin biopsy sites for NMSC requires (i) invisibility under ambient light, (ii) fluorescence under a selective light source, (iii) a finite intradermal retention time (ca. 3 months), and (iv) biocompatibility. Herein, we introduce cross-linked fluorescent supramolecular nanoparticles (c-FSNPs) as a "finite tattoo" pigment, with optimized photophysical properties and intradermal retention time to achieve successful in vivo finite tattooing. Fluorescent supramolecular nanoparticles encapsulate a fluorescent conjugated polymer, poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene] (MPS-PPV), into a core via a supramolecular synthetic approach. FSNPs which possess fluorescent properties superior to those of the free MPS-PPV are obtained through a combinatorial screening process. Covalent cross-linking of FSNPs results in micrometer-sized c-FSNPs, which exhibit a size-dependent intradermal retention. The 1456 nm sized c-FSNPs display an ideal intradermal retention time (ca. 3 months) for NMSC lesion labeling, as observed in an in vivo tattoo study. In addition, the c-FSNPs induce undetectable inflammatory responses after tattooing. We believe that the c-FSNPs can serve as a "finite tattoo" pigment to label potential malignant NMSC lesions.

Hole-Transporting Materials Based on Twisted Bimesitylenes for Stable Perovskite Solar Cells with High Efficiency.

A new class of hole-transport materials (HTMs) based on the bimesitylene core designed for mesoporous perovskite solar cells is introduced. Devices fabricated using two of these derivatives yield higher open-circuit voltage values than the commonly used spiro-OMeTAD. Power conversion efficiency (PCE) values of up to 12.11% are obtained in perovskite-based devices using these new HTMs. The stability of the device made using the highest performing HTM (P1) is improved compared with spiro-OMeTAD as evidenced through long-term stability tests over 1000 h.

Structurally Flexible C3-Symmetric Receptors for Molecular Recognition and Their Self-Assembly Properties.

The bioinspired design and synthesis of building blocks and their assemblies by the supramolecular approach has ever fascinated scientists to utilize such artificial systems for numerous purposes. Flexibility is a basic feature of natural systems. However, in artificial systems this is difficult to control, especially if there is no preorganization of the component(s) of a system. We have designed and synthesized a series of C3 -symmetric N-bridged flexible receptors and successfully utilized them to selectively entrap the notorious and toxic nitrate anion in aqueous medium. This was the first report of highest binding affinity for the nitrate anion in aqueous medium. An impressive self-sorting phenomenon of reversibly formed hydrogen-bonded capsules, which self-assembled from flexible tripodal receptors having branches of similar size and bearing the same amide functionality, has been disclosed. Encapsulated nitrate anion has been further utilized for the photochemical [2+2] cycloaddition reaction for the synthesis of strained four-membered ring structures through dynamic self-assembly. In this Personal Account, we summarize these results showing the utility of naturally inspired flexibility in artificial systems.