Due to the chemical stability of graphene, synthesis of carboxylated graphene still remains challenging during the electrochemical exfoliation of graphite. In this work, a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets for the electrochemical synthesis of highly stable carboxylated graphene is reported. Here, formate anions act as both intercalation ions and co-reactant acid for the confinement of electro-generated carboxylic radical (âCOOH) in the sub-nanometer scaled interlayers, which facilitates the radical addition reaction on graphene sheets. The controllable carboxylation of graphene is realized by tuning the concentration of formate anions in the electrolyte solution. The high crystallinity of the obtained product indicates the occurrence of spatially confined âCOOH addition reaction between the sub-nanometer interlayers of expanded graphite. In addition, the carboxylated graphene have been used for water desalination and hydrogen/oxygen reduction reaction. Therefore, this work provides a new method for the in situ preparation of functionalized graphene through the electrolysis and its applications in water desalination and hydrogen/oxygen reduction reactions.
As model catalysts, it is necessary to study the relationship between the structure and properties of ultra-small metal nanoclusters (MNCs) and to reduce their steric hindrance as much as possible, e.g. preparing ultrasmall MNCs protected by ultra-short ligands. However, it is challenging to attain various MNCs with the same cores but different surface stabilizing ligands. Additionally, shortening the chains of protecting ligands will lead to larger MNC cores. Here, four different Pd NCs (Pd6(SC4H9)12, Pd6(SC8H17)12, Pd6(SC6(C2)H17)12 and Pd6(SC6H13)12) were successfully synthesized by a slow synthesis process. All these clusters consist of six Pd atoms and are stabilized by 12 thiols with different chain lengths and steric hindrance. The catalytic properties of the as-prepared Pd6 NCs were evaluated using the catalytic reduction of p-nitroaniline to p-phenylenediamine as a model reaction. The outcomes indicated that shortening the chain length of the protecting thiols could enhance the catalytic activity of the Pd6 NCs. Notably, stable and active ultra-small Pd6 clusters stabilized by ultra-short ligands (HSC4H9) were successfully synthesized. Although the performance of Pd6(SC4H9)12 clusters protected by the ultra-short thiols is lower than that of commercial palladium on carbon (Pd/C), they display higher stability. Interestingly, the activity of Pd6 NCs protected by ethyl-branched alkane thiols is also better than that of Pd6 NCs protected by the alkane thiol ligands with the same chain length or the same number of carbon numbers. This work provides clear evidence that the catalytic activity of atomically precise MNCs can be controlled by regulating the surface stabilizing ligands.
It is highly challenging to activate the basal plane and minimize the π-π stacking of MoS2 sheets, thus enhancing its catalytic performance. Here, we display an approach for making well-dispersed MoS2 . By using the N-doped multi-walled carbon nanotubes (NMWCNTs) as an isolation unit, the aggregation of MoS2 sheets was effectively reduced, favoring the dispersion of Pt nanoparticles (noted as Pt/NMWCNTs-isolated-MoS2 ). Excellent bifunctional catalytic performance for methanol oxidation and oxygen reduction reaction (MOR/ORR) were demonstrated by the produced Pt/NMWCNTs-isolated-MoS2 . In comparison to Pt nanoparticles supported on MoS2 (Pt/MoS2 ), the MOR activity (2314.14â mA mgpt -1 ) and stability (317.69â mA mgpt -1 after 2â h of operation) on Pt/NMWCNTs-isolatedMoS2 were 24 and 232 times higher, respectively. As for ORR, Pt/NMWCNTs-isolated-MoS2 holds large half-wave potential (0.88â V) and high stability (92.71 % after 22â h of operation). This work presents a tactic for activating the basal planes and reducing the π-π stacking of 2D materials to satisfy their applications in electrocatalysis. In addition, the proposed sheet-isolation method can be used for fabricating other 2D materials to promote the dispersion of nanoparticles, which assist its application in other fields of energy as well as the environment.
Flexible piezoelectric materials capable of withstanding large deformation play key roles in flexible electronics. Ferroelectric ceramics with a high piezoelectric coefficient are inherently brittle, whereas polar polymers exhibit a low piezoelectric coefficient. Here we report a highly stretchable/compressible piezoelectric composite composed of ferroelectric ceramic skeleton, elastomer matrix and relaxor ferroelectric-based hybrid at the ceramic/matrix interface as dielectric transition layers, exhibiting a giant piezoelectric coefficient of 250 picometers per volt, high electromechanical coupling factor keff of 65%, ultralow acoustic impedance of 3MRyl and high cyclic stability under 50% compression strain. The superior flexibility and piezoelectric properties are attributed to the electric polarization and mechanical load transfer paths formed by the ceramic skeleton, and dielectric mismatch mitigation between ceramic fillers and elastomer matrix by the dielectric transition layer. The synergistic fusion of ultrahigh piezoelectric properties and superior flexibility in these polymer composites is expected to drive emerging applications in flexible smart electronics.
Tailor-made metal oxide/hydroxide core-shell structures are promising for the fabrication of effective electrocatalysts. Here, we report the development of a core-shell structure based on carbon-doped and Ni(OH)2 nanofilms wrapped ZnO microballs (NFs-Ni(OH)2 /ZnO@C MBs) for glucose and hydrogen peroxide (H2 O2 ) monitoring. The unique ball-like morphology of the designed structure is achieved through a facile solvothermal strategy by the control of reaction conditions. Typically, ZnO@C MBs offer highly conductive core, and the shell of Ni(OH)2 nanofilms increases the density of catalytic active sites. The interesting morphology and the brilliant electrocatalytic efficacy of designed hybrid, encourage us to design a multi-mode sensor for glucose and H2 O2 screening. The NFs-Ni(OH)2 /ZnO@C MBs/GCE glucose sensor presented good sensitivities (647.899 & 161.550â µA (mmol L-1 )-1 cm-2 ), a quick response (<4â s), lower limit of detection (0.04â µmol L-1 ), and wide detection range (0.004-1.13 & 1.13-5.02â mmol L-1 ). Similarly, the same electrode revealed excellent H2 O2 sensing features including good sensitivities, two linear parts of 3.5-452 and 452-1374â µmol L-1 , and detection limit of 0.03â µmol L-1 as well as high selectivity. Thus, the development of novel hybrid core-shell structure is useful for potential applications in glucose and H2 O2 screening from environmental and physiological samples.
Anion-exchange membrane fuel cells and Zn-air batteries based on non-Pt group metal catalysts typically suffer from sluggish cathodic oxygen reduction. Designing advanced catalyst architectures to improve the catalyst's oxygen reduction activity and boosting the accessible site density by increasing metal loading and site utilization are potential ways to achieve high device performances. Herein, we report an interfacial assembly strategy to achieve binary single-atomic Fe/Co-Nx with high mass loadings through constructing a nanocage structure and concentrating high-density accessible binary single-atomic Fe/Co-Nx sites in a porous shell. The prepared FeCo-NCH features metal loading with a single-atomic distribution as high as 7.9 wt% and an accessible site density of around 7.6 × 1019 sites g-1, surpassing most reported M-Nx catalysts. In anion exchange membrane fuel cells and zinc-air batteries, the FeCo-NCH material delivers peak power densities of 569.0 or 414.5 mW cm-2, 3.4 or 2.8 times higher than control devices assembled with FeCo-NC. These results suggest that the present strategy for promoting catalytic site utilization offers new possibilities for exploring efficient low-cost electrocatalysts to boost the performance of various energy devices.
Bifunctional oxygen electrocatalysts that hold outstanding activity and stability are highly crucial for the development of efficient rechargeable Zn-air batteries. Herein, cobalt-molybdenum-based bimetallic carbide and cobalt nanoparticles embedded N-doped carbon nanocages are synthesized via the pyrolysis of functionalized zeolitic imidazolate framework precursor originated from zeolitic imidazolate framework sequentially coated with polydopamine and phosphomolybdic acid. Furthermore, we revealed the composition-performance relationship based on the exploration of bifunctional performance on the pyrolysis products. More importantly, the synergy of multiple active sites with hollow structure gives the prepared catalyst a low overpotential (284 mV) for oxygen evolution reaction and high half-wave potential (0.865 V) for oxygen reduction reaction, besides an excellent bifunctional durability. Furthermore, the prepared catalyst as a cathode electrocatalyst grants the assembled rechargeable Zn-air batteries a high open-circuit voltage, power density, specific capacity, and remarkable charge-discharge cycle stability. This work provides a strategy for the integration and active-adjustment of bifunctional catalyst and its potential applications in water splitting and other catalytic reactions.
The miniaturization of electronic devices and power systems for capacitive energy storage under harsh environments requires scalable high-quality ultrathin high-temperature dielectric films. To meet the need, ultrasonic spray-coating (USC) can be used. Novel polyimides with a dipolar group, CF3 (F-PI), and all-organic composites with trace organic semiconductor can serve as models. These scalable high-quality ultrathin films (≈2.6 and ≈5.2 µm) are successfully fabricated via USC. The high quality of the films is evaluated from the micro-millimeter scale to the sub-millimeter and above. The high glass transition temperature Tg (≈340 °C) and concurrent large bandgap Eg (≈3.53 eV) induced by weak conjugation from considerable interchain distance (≈6.2 Å) enable F-PI to be an excellent matrix delivering a discharge energy density with 90% discharge efficiency Uη90 of 2.85 J cm-3 at 200 °C. Further, the incorporation of a trace organic semiconductor leads to a record Uη90 of ≈4.39 J cm-3 at 200 °C due to the markedly enhanced breakdown strength caused by deep charge traps of ≈2 eV. Also, a USC-fabricated multilayer F-PI foil capacitor with ≈85 nF (six layers) has good performance at 150 °C. These results confirm that USC is an excellent technology to fabricate high-quality ultrathin dielectric films and capacitors.
Triboelectric charge density and energy density are two crucial factors to assess the output capability of dielectric materials in a triboelectric nanogenerator (TENG). However, they are commonly limited by the breakdown effect, structural parameters, and environmental factors, failing to reflect the intrinsic triboelectric behavior of these materials. Moreover, a standardized strategy for quantifying their maximum values is needed. Here, by circumventing these limitations, we propose a standardized strategy employing a contact-separation TENG for assessing a dielectric material's maximum triboelectric charge and energy densities based on both theoretical analyses and experimental results. We find that a material's vacuum triboelectric charge density can be far higher than previously reported values, reaching a record-high of 1250 µC m-2 between polyvinyl chloride and copper. More importantly, the obtained values for a dielectric material through this method represent its intrinsic properties and correlates with its work function. This study provides a fundamental methodology for quantifying the triboelectric capability of dielectric materials and further highlights TENG's promising applications for energy harvesting.
Oilseed rape (Brassica napus) has significant heterosis and Ogura CMS is a major way to use it. Ogura CMS has the advantages of complete and stable male sterility and easy-to-breed maintainers. Therefore, to breed better restorers has become an important goal for this system. Incidentally, clubroot is a soil-borne disease that is difficult to control by fungicidal chemicals, and it has been the main disease of oilseed rape in recent years in China, severely restricting the development of the oilseed rape industry. At present, the most effective method for controlling clubroot disease is to cultivate resistant varieties. One Ogura CMS restorer line (R2163) has shown much better combining ability, but lacks the clubroot disease resistance. This study was carried out to improve R2163 through marker-assisted backcross breeding (MABB). The resistant locus PbBa8.1 was introduced into the restorer R2163, and we then selected R2163R with clubroot disease resistance. Using the new restorer R2163R as the male parent and the sterile lines 116A and Z11A as the female parent, the improved, new resistant hybrids Kenyouza 741R and Huayouza 706R performed well, providing strong resistance and good agronomic traits. This work advances the utilization of heterosis and breeding for clubroot disease resistance in B. napus.
The controllable synthesis of 1-dimensional (1D) multi-metal Pt-based alloys, with enhanced electro-chemical properties remains a challenge, despite the wide application of Pt-based catalysts in fuel cells and in the hydrogen evolution reaction (HER). Herein, we fabricate PtCuFe alloy nanochains (NCs) that have a tunable composition by flexibly adjusting the molar ratios of the metal precursors. It was found that Cu2+ is key in the formation of 1D NCs, as confirmed by transmission electron microscopy characterizations. In addition, the alloyed Fe can further increase the content of the metallic state of Cu in the PtCuFe NCs. The as-prepared PtCuFe NCs exhibited higher catalytic activity and stability than those of the Pt nanoparticles (NPs), PtFe NPs, and PtCu NCs, for the methanol oxidation reaction (MOR) and HER. Additionally, the composition-performance relationship of PtCuxFey NCs toward the MOR and HER were investigated. The hybrid density functional theory calculation and analysis showed that the 1D PtCuFe NCs have a lower lowest unoccupied molecular orbital (LUMO) than those of the 2- and 3-dimensional PtCuFe, verifying that the 1D PtCuFe NCs exhibit the highest activity for the MOR. This work has established a new method for the controllable synthesis of multi-metal Pt-based NCs/alloy catalysts and their subsequent applications in other electro-catalytic reactions.
In recent years, based on the high catalytic activities of metal nanoclusters (MNCs) and the unique porous structure of metal-organic frameworks (MOFs), much work has focused on MOF-confined small MNCs for catalysis applications. However, the commonly used "ship-in-boat" approach is unfeasible for precisely controlling the size and composition of the formed MNCs and meanwhile often causes structural distortion/degradation. On the other hand, the "bottle-around-ship" method usually has the disadvantages that MOFs show uncontrollable self-nucleation outside the MNCs and the stabilizers on the surface of MNCs may greatly reduce their catalytic activities. In this work, monodispersed Pt16(C4O4SH5)26 clusters (Pt16(MSA)26) were first prepared and used as a precursor for the synthesis of Pt(MSA)@ZIF-67 via the typical Co-carboxylate type of linkage at the interface under ambient atmosphere. After encapsulating the Pt clusters in ZIF-67, the protecting ligands were removed under 300 °C to get surface-clean Pt16 clusters confined in ZIF-67 (Pt@ZIF-67). The obtained Pt@ZIF-67 exhibited high catalytic activity for the hydrolysis of ammonia borane that was superior to that of most of the reported noble-metal catalysts. Meanwhile, by annealing the Pt(MSA)@ZIF-67 at 800 °C to form highly conductive graphitic carbon-coated Pt NCs and Co nanoparticles (NPs) (Pt/Co@NC), the obtained composite showed high catalytic activity for the oxygen reduction reaction (ORR). The formed Pt/Co@NC showed 9.6 times higher ORR mass activity (at 0.8 V) than Pt/C. This work provides a strategy to fabricate highly dispersed and stable metal clusters confined in the porous matrix for catalysis and shows that highly porous MOFs have promising catalysis applications by combining them with other active components.
Human bodily kinesthetic sensing is generally complicated and ever-changing due to the diversity of body deformation as well as the complexity of mechanical stimulus, which is different from the unidirectional mechanical motion. So, there exists a huge challenge for current flexible sensors to accurately differentiate and identify what kind of external mechanical stimulus is exerted via analyzing digital signals. Here, we report a flexible dual-interdigital-electrode sensor (FDES) that consists of two interdigital electrodes and a highly pressure-sensitive porous conductive sponge. The FDES can precisely identify multiple mechanical stimuli, e.g., pressing, positive bending, negative bending, X-direction stretching, and Y-direction stretching, and convert them into corresponding current variation signals. Moreover, the FDES exhibits other exceptional properties, such as high sensitivity, stretchability, large measurement range, and outstanding stability, accompanied by simple structural design and low-cost processing simultaneously. Additionally, our FDES successfully identifies various complex activities of the human body, which lays a foundation for the further development of multimode flexible sensors.
Biosensing Techniques/instrumentation , Biosensing Techniques/methods , Electric Conductivity , Electrodes , Monitoring, Physiologic/methods , Wearable Electronic Devices , Humans , Pressure , Tensile Strength
Flexible pressure sensors have emerged as an indispensable part of wearable devices due to their application in physiological activity monitoring. To realize long-term on-body service, they are increasingly required for properties of conformability, air permeability, and durability. However, the enhancement of sensitivity remains a challenge for ultrathin capacitive sensors, particularly in the low-pressure region. Here, we introduced a highly sensitive and ultrathin capacitive pressure sensor based on a breathable all-fabric network with a micropatterned nanofiber dielectric layer, an all-fabric capacitive sensor (AFCS). This all-fabric network endows a series of exceptional performances, such as high sensitivity (8.31 kPa-1 under 1 kPa), ultralow detection limit (0.5 Pa), wide detection range (0.5 Pa to 80 kPa), and excellent robustness (10â¯000 dynamic cycles). Besides, the all-fabric structure provides other properties for the AFCS, e.g., high skin conformability, super thinness (dozens of micrometers), and exceptional air permeability. Our AFCS shows promising potential in breathing track, muscle activity detection, fingertip pressure monitoring, and spatial pressure distribution, paving way for comfortable skinlike epidermal electronics.
Monitoring, Physiologic/instrumentation , Nanofibers/chemistry , Wearable Electronic Devices , Electric Capacitance , Equipment Design , Humans , Sensitivity and Specificity
Through a two-way control of hexadecyl trimethyl ammonium bromide (CTAB) and hydrochloric acid (HCl), the PdCu nanoalloys with branched structures are synthesized in one step by hydrothermal reduction and used as electrocatalysts for formic acid oxidation reaction (FAOR). In this two-way control strategy, the CTAB is used as a structure-oriented surfactant, while a certain amount of HCl is used to control the reaction kinetics for achieving gradual growth of multi-dendritic structures. The characterizations including scanning transmission electron microscope (STEM), X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) suggest that PdCu nanoalloys with unique multi-dendritic branches have favorable electronic structure and lattice strain for electrocatalyzing the oxidation of formic acid. In specific, among the electrocatalysts with different Pd/Cu ratios, the Pd1Cu1 branched nanoalloys have the largest electrochemically active surface area (ECSA) and the best performance for the FAOR. The catalytic activity of the Pd1Cu1 branched nanoalloys is 2.4 times that of commercial Pd black. After the chronoamperometry test, the Pd1Cu1 branched nanoalloys still maintain their original morphologies and higher current density than that of the commercial Pd black. In addition, in the CO-stripping tests, the initial oxidation potential and the oxidation peak potential of the PdCu branched nanoalloys for CO adsorption are lower than those of commercial Pd balck, evincing their better anti-poisoning performance.
Formates , Adsorption , Cetrimonium , Oxidation-Reduction
High luminescence intensity from materials that are excited by external stimuli is highly desired. In this work, a stretchable hybrid luminescent composite (HLC) that has multiple luminescence modes is reported. The luminescence can be excited either by externally applied mechanical strain or by a moving object that slides against the HLC. When the HLC is deformed, such as being twisted or folded, the ZnS/Cu phosphor experiences mechanical strain that trigger the mechanoluminescence (ML) of the phosphors. Moreover, as the HLC slides against a contact object, the triboelectrification at the contact interface induces the electroluminescence of phosphor. Here, a series of internal and external factors were studied on how they influence the luminescent intensity. It is found that the luminescent intensity from the two modes can be superposed. The HLC material was used to fabricate a fiber-based luminescent device that can be driven by air flow. The overall luminescent intensity is enhanced by over 72% compared to that obtained solely from the ML. The HLC reported in this work has such potential applications as self-powered light sources and sensors as means of detecting dynamic motions and interaction.
BACKGROUND: Snap bean, Phaseolus vulgaris L., as a warm-season vegetable, low temperature stress seriously affect the yield and quality. At present, little is known about the genes and molecular regulation mechanism in cold response in snap bean exposed to low temperature. OBJECTIVES: Our objectives were to identify the low temperature response genes in snap bean and to examine differences in the gene response between cold-tolerant and cold-sensitive genotypes. METHODS: We used two highly inbred snap bean lines in this study, the cold-tolerant line '120', and the cold-sensitive line '093'. The plants were grown to the three leaf and one heart stage and exposed to 4 °C low temperature. We used RNA sequencing (RNA-seq) to analyze the differences of gene expression. RESULTS: 988 and 874 cold-responsive genes were identified in 'T120 vs CK120' and 'T093 vs CK093' ('T' stands for low temperature treatment, and 'CK' stands for control at room temperature), respectively. Of these, 555 and 442 genes were unique to cold-stressed lines '120' and '093', respectively compared to the control. Our analysis of these differentially expressed genes indicates that Ca2+, ROS, and hormones act as signaling molecules that play important roles in low temperature response in P. vulgaris. Altering the expression of genes in these signaling pathways activates expression of downstream response genes which can interact with other signaling regulatory networks. This may maintained the balance of ROS and hormones, making line '120' more cold-tolerant than line '093'. CONCLUSION: Our results provide a preliminarily understanding of the molecular basis of low temperature response in snap bean, and also establish a foundation for the future genetic improvement of cold sensitivity in snap bean by incorporating genes for cold tolerance.
Cold Temperature , Cold-Shock Response/genetics , Phaseolus/genetics , Transcriptome , Calcium Signaling , Metabolic Networks and Pathways/genetics , Phaseolus/metabolism , Plant Growth Regulators/physiology , Reactive Oxygen Species/metabolism , Transcription Factors/genetics , Transcription Factors/metabolism
A fully rollable nanocomposite-based nanogenerator (NCG) is developed by integrating a lead-free piezoelectric hybrid layer with a type of nanofiber-supported silver nanowire (AgNW) network as electrodes. The thin-film nanocomposite is composed of electroactive polyvinylidene fluoride (PVDF) polymer matrix and compositionally modified potassium sodium niobate-based nanoparticles (NPs) with a high piezoelectric coefficient ( d33) of 53 pm/V, which is revealed by the piezoresponse force microscopy measurements. Under periodical agitation at a compressive force of 50 N and 1 Hz, the NCG can steadily render high electric output up to an open-circuit voltage of 18 V and a short-circuit current of 2.6 µA. Of particular importance is the decent rollability of the NCG, as indicated by the negligible decay in the electric output after it being repeatedly rolled around a gel pen for 200 cycles. Besides, the biocompatible NCG can potentially be used to scavenge biomechanical energy from low-frequency human motions, as demonstrated by the scenarios of walking and elbow joint movement. These results rationally expand the feasibility of the developed NCG toward applications in lightweight, diminutive, and multifunctional rollable or wearable electronic devices.
A novel nanostructured catalyst of platinum nanoparticles supported on 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) functionalized graphene (TMPyP-graphene) is synthesized by the hydrothermal polyol process. The as-synthesized nanocomposites are characterized by Fourier transform infrared (FTIR) spectroscopy, UV-vis absorption spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical tests. It has been found that Pt nanoparticles of ca. 3.4 nm are uniformly dispersed on the surface of TMPyP-graphene, and hold a high electrochemical active surface area (ECSA) of 126.2 m(2) g(-1). The results demonstrate that the Pt/TMPyP-graphene catalyst exhibits a much higher electrocatalytic activity and stability than the Pt/graphene and commercial Pt/C catalysts for methanol oxidation, which is of significant importance in improving the efficiency of Pt-based electrocatalysts for DMFCs applications.
A series of Cu(I) complexes with a [Cu(NN)(PP)](+) moiety, [Cu(phen)(pba)](BF(4)) (1a), [Cu(2)(phen)(2)(pbaa)](BF(4))(2) (2a), [Cu(2)(phen)(2)(pnaa)](BF(4))(2) (3a), [Cu(2)(phen)(2)(pbbaa)](BF(4))(2) (4a), [Cu(dmp)(pba)](BF(4)) (1b), [Cu(2)(dmp)(2)(pbaa)](BF(4))(2) (2b), [Cu(2)(dmp)(2)(pnaa)](BF(4))(2) (3b) and [Cu(2)(dmp)(2)(pbbaa)](BF(4))(2) (4b) (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, pba = N,N-bis((diphenylphosphino)methyl)benzenamine, pbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine, pnaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)naphthalene-1,5-diamine and pbbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)biphenyl-4,4'-diamine), were rationally designed and synthesized. These complexes were characterized by (1)H and (31)P NMR, electrospray mass spectrometry, elemental analysis and X-ray crystal structure analysis. Introduction of different central arene spacers (phenyl, naphthyl, biphenyl) into ligands, resulting in the size variation of these complexes, aims to tune the photophysical properties of the complexes. Each Cu(I) ion in these complexes adopts a distorted tetrahedral geometry constructed by the chelating diimine and phosphine groups. Intermolecular C-H···π and/or π···π interactions are involved in the solid states. The dmp-containing complex exhibits better emission relative to the corresponding phen complex due to the steric encumbrance of bulky alkyl groups. Furthermore, for complexes with identical diimine but different phosphine ligands, the tendency of increased emission lifetime as well as blue-shifted emission in the solid state follows with the decrease in size of complexes. Intermolecular C-H···π interactions have an influence on the final solid state photophysical properties through vibrationally relaxed non-radiative energy transfer in the excited state. Smaller-sized complexes show better photophysical properties due to less vibrationally relaxed behavior related to flexible C-H···π bonds. Nevertheless, the tendency for increased quantum yield and emission lifetime, as well as blue-shifted emission in dilute solution goes with the increase in size of complexes. The central arene ring (phenyl, naphthyl or biphenyl) has an influence on the final photophysical properties. The larger the π-conjugated extension of central arene ring is, the better the photophysical properties of complex are. The rigid and large-sized complex 3b, with a high quantum yield and long lifetime, is the best luminophore among these complexes.
