Nonbonding Electron Delocalization Stabilizes the Flexible N8 Molecular Assembly.

Electron delocalization has an important impact on the physical properties of condensed materials. However, the L-electron delocalization in inorganic, especially nitrogen, compounds needs exploitation to improve the energy efficiency, safety, and environmental sustainability of high-energy-density materials (HEDMs). This Letter presents an intriguing N8 molecule, ingeniously utilizing nitrogen's L-electron delocalization. The molecule, exhibiting a unique lollipop-shaped conformation, can fold at various angles with very low energy barriers, self-assembling into environmentally stable, all-nitrogen crystals. These crystals demonstrate unparalleled stability, high energy density, low mechanical sensitivity, and optimal electronic thermal conductivity, outperforming existing HEDMs. The remarkable properties of these designed materials are attributed to two distinct delocalized systems within nitrogen's L-shell: π- and lone pair σ-electrons, which not only stabilize the molecular structure but also facilitate interconnected 3D networks of intermolecular nonbonding interactions. This work might pave the way to the experimental synthesis of environmentally stable all-nitrogen solids.

Molecular Engineering Modulating the Singlet-Triplet Energy Splitting of Indolocarbazole-Based TADF Emitters Exhibiting AIE Properties for Nondoped Blue OLEDs with EQE of Nearly 20.

The development of efficient blue thermally activated delayed fluorescence (TADF) emitters with an aggregation-induced emission (AIE) nature, for the construction of organic light-emitting diodes (OLEDs), is still insufficient. This can be attributed to the challenges encountered in molecular design, including the inherent trade-off between radiative decay and reverse intersystem crossing (RISC), as well as small singlet-triplet energy splitting (ΔEST) and the requirement for high photoluminescence quantum yields (ΦPL). Herein, we present the design of three highly efficient blue TADF molecules with AIE characteristics by combining π-extended donors with different acceptors to modulate the differences in the electron-donating and electron-withdrawing abilities. This approach not only ensures high emission efficiency by suppressing close π-π stacking, weakening nonradiative relaxation, and enhancing radiative transition but also maintains the equilibrium ratio between the triplet and singlet excitons by facilitating the process of RISC. These emitters exhibit AIE and TADF properties, featuring quick radiative rates and low nonradiative rates. The ΦPL of these emitters reached an impressive 88%. Based on their excellent comprehensive performance, nondoped PICzPMO and PICzPMO OLEDs achieved excellent electroluminescence performance, exhibiting maximum external quantum efficiency (EQEmax) of up to 19.5%, while the doped device achieved a higher EQEmax of 20.8%. This work demonstrated that by fusing π-extended large rigid donors with different acceptors, it is possible to regulate the difference in electron-donating and electron-withdrawing abilities, resulting in a small ΔEST, high ΦPL, and fast RISC process, which is a highly feasible strategy for designing efficient TADF molecules.

Seedless wet synthesis of copper-twinned nanocrystals.

The wet synthesis of copper (Cu)-twinned nanostructures often requires the addition of noble metal seeds, as twinned Cu seeds are prone to oxidative etching, which inevitably introduces other metal species. In this study, a universal and seedless wet method is proposed for the synthesis of various Cu-twinned nanostructures, such as large Cu decahedrons (with sizes up to 300 nm), singly twinned Cu right bipyramids, and Cu nanorods. The amount of chloride ions (Cl-) and oleylamine and an optimal heating rate at the initial stage were proven to be crucial in this synthesis. Theoretical results revealed that the amount of Cl- could adjust the Gibbs free energy of Cu seeds by promoting the dissociation of oleylamine, which, in turn, determined the structure of thermodynamically favorable seeds based on the thermodynamic model. To the best of our knowledge, this is the first report on large Cu decahedrons and singly twinned Cu right bipyramids. Moreover, they both showed strong localized surface plasmon resonance in the near-infrared region. The photothermal conversion efficiency of large Cu decahedrons increased up to 52.9% upon 808 nm laser irradiation, which is the highest value ever reported for Cu nanocrystals.

Controllable Gold Nanocluster-Emulsion Interface for Direct Cell Penetration and Photothermal Killing.

In the view of their ability to be uptaken by cells, colloidal particles can exert diverse physiological effects and are promising vehicles for the intracellular delivery of biologically active substances. Given that the modulation of biomaterial interfaces greatly facilitates the prediction and control of the corresponding cellular responses, the interfacial behavior of hydrophobic dye-modified gold (Au) nanoclusters (Au NCs) is rationally designed to develop Au NC-containing emulsions and control their biointerfacial interactions with cell membranes. The observed biological performance is indicative of a physical penetration mechanism. The amphiphilic Au NCs decrease the interfacial energy of two immiscible liquids and hinder droplet coalescence to facilitate the formation of emulsions thermodynamically stabilized by dipole-dipole and hydrophobic interactions. Moreover, the amphiphilic Au NCs are localized on the emulsion droplet surface and form segregated interfacial microdomains that adapt to the membrane structure and facilitate the traverse of the emulsions across the cell membrane via direct penetration. Fast penetration coupled with excellent photophysical performance endows the emulsions with multifluorescence tracing and efficient photothermal killing capabilities. The successful change of the interaction mode between NCs and biological objects and the provision of a universal formulation to modulate biointerfacial interactions are expected to inspire new bioapplications.

Chloride-ion-directed synthesis of plate-like Cu2O mesocrystals for effective nitrogen fixation.

Cuprous oxide (Cu2O) mesocrystals, which are composed of numerous nanocrystals with a common crystallographic orientation, are supposed to possess superior photocatalytic abilities than the normal constructions, but very few of them have been reported to date. In this work, plate-like Cu2O mesocrystals were successfully fabricated via a facile one-pot wet chemical strategy. Unlike the commonly used polymers or small molecules, chloride ions (Cl-) were employed as structure-directing agents and played the main role in the Cu2O mesocrystal formation. The formation mechanism was interpreted as follows: the presence of Cl- inhibited the formation of CuO and Cu by forming the intermediate product CuCl, which was further hydrolyzed to Cu2O nanocrystals. Cl- tended to adsorb on the (111) facets of the formed Cu2O nanocrystals and stabilize them. Then the Cu2O nanocrystals were aligned side by side through the unabsorbed side faces, leading to mutual nanocrystals orientation and crystallographic lock-in, facilitating the formation of plate-like Cu2O mesocrystals. The polymer, polyacrylamide (PAM), also promoted the mesocrystals formation by serving as a stabilizer and fixed the crystallographic orientation of the Cu2O nanocrystals during their orderly stacking process. The plate-like Cu2O mesocrystals showed a long decay time and pronounced performance toward the visible-light-driven photocatalytic reduction of N2 into NH3. This research may stimulate in-depth investigations into the exploration of new synthetic methods for the design and construction of novel mesocrystals.

Conjugated Molecule-Assisted Supramolecular Hydrogel with Enhanced Antibacterial and Antibiofouling Properties.

The hydrogel using natural and synthetic polymers to create a cross-linking network has drawn attention in diverse bioapplications. However, inhibition of bacterial infection is still a challenge for hydrogel's wide application. In this work, we reported a supramolecular hydrogel with a good antibacterial property built from conjugated molecules. The water-soluble molecular 4,7-bis[9,9-di(2-carboxy-ethyl)-fluoren-2-yl]-2,1,3-benzothiadiazole (OFBTCOOH) physically linked with monomers via hydrophobic interaction. The free-radical polymerized poly(N-acryloyl glycinamide) was hydrogen-bond cross-linked by dual amides in the side chains to form a hydrogel. An adjustable micro-network was obtained by increasing OFBTCOOH with evidence of enhanced intermolecular interaction. The successfully integrated OFBTCOOH could be excited upon light irradiation. The energy of triplet-state excitons of OFBTCOOH transferred to the ground-state oxygen to produce singlet oxygen, which endowed the hydrogel with the antibacterial property. Meanwhile, the superhydrophilic surface of the hydrogel can bind water molecules to form a stable hydration layer, which acted as barriers to resist protein and bacterial adsorption and achieve the anti-biofouling goal. The ease in introducing conjugated polyelectrolytes may provide a formulation to functionalize hydrogels via various physical interactions.

Controlling the Interaction between Fluorescent Gold Nanoclusters and Biointerfaces for Rapid Discrimination of Fungal Pathogens.

Nondestructive detection and discrimination of fungal pathogens is essential for rapid and precise treatment, which further effectively prevents antifungal resistance from overused drugs. In this work, fluorescent gold nanoclusters served as the basis for discriminating Candida species. Varied on surface ligands, these gold nanoclusters demonstrated different optical properties as a result of the perturbation effects of ligands. The biointerface interaction between the surface ligands of gold nanoclusters and the cell walls of Candida species can be constructed, and their restriction on ligands perturbation effect produced enhanced fluorescence signals. Owing to the variation of the cell wall composition, cells of different Candida species demonstrated different degrees of association with the gold nanoclusters, leading to discriminable amounts of fluorescence enhancements. The reverse signal response from these gold nanoclusters gives rise to a synergistic and effective assay that allows identification of Candida species.

Detecting Air Pollutant Molecules Using Tube-Shaped Single Electron Transistor.

An air pollution detector is proposed based on a tube-shaped single-electron transistor (SET) sensor. By monitoring the flow control component of the detector, each air pollutant molecule can be placed at the center of a SET nanopore and is treated as an island of the SET device in the same framework. Electron transport in the SET was incoherent, and the performances of the SET were sensitive at the single molecule level. Employing first-principles calculations, electronic features of an air pollutant molecule within a tube-shaped SET environment were found to be independent of the molecule rotational orientations with respect to axis of symmetry, unlike the electronic features in a conventional SET environment. Charge stability diagrams of the island molecules were demonstrated to be distinct for each molecule, and thus they can serve as electronic fingerprints for detection. Using the same setup, quantification of the air pollutant can be realized at room temperature as well. The results presented herein may help provide guidance for the identification and quantification of various types of air pollutants at the molecular level by treating the molecule as the island of the SET component in the proposed detector.

Effective Design Strategy for Aggregation-Induced Emission and Thermally Activated Delayed Fluorescence Emitters Achieving 18% External Quantum Efficiency Pure-Blue OLEDs with Extremely Low Roll-Off.

High-color purity organic emitters with a simultaneous combination of aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) characteristics are in great demand due to their excellent comprehensive performances toward efficient organic light-emitting diodes (OLEDs). In this work, two D-π-A-structure emitters, ICz-DPS and ICz-BP, exhibiting AIE and TADF properties were developed, and both the emitters have narrow singlet (S1)-triplet (T1) splitting (ΔEST) and excellent photoluminescence (PL) quantum yields (ΦPL), derived from the distorted configurations and weak intra/intermolecular interactions, suppressing exciton annihilation and concentration quenching. Their doped OLEDs based on ICz-BP provide an excellent electroluminescence external quantum efficiency (ηext) and current efficiency (ηC) of 17.7% and 44.8 cd A-1, respectively, with an ηext roll-off of 2.9%. Their nondoped OLEDs based on ICz-DPS afford high efficiencies of 11.7% and 30.1 cd A-1, with pure-blue emission with Commission Internationale de l'Éclairage (CIE) coordinates of (0.15, 0.08) and a low roll-off of 6.0%. This work also shows a strategy for designing AIE-TADF molecules by rational use of steric hindrance and weak inter/intramolecular interactions to realize high ΦPL values, fast reverse intersystem crossing process, and reduced nonradiative transition process properties, which may open the way toward highly efficient and small-efficiency roll-off devices.

Effect of incremental increase in radial neck height on coronoid and capitellar contact pressures.

BACKGROUND: Over-lengthening of the radial neck has been shown to affect ulnohumeral kinematics and has been proposed to affect radiocapitellar pressures. We hypothesized that an incremental increase in radial neck height increases the capitellar contact pressure and reduces the coronoid contact pressure. Knowledge of the effects of over-lengthening is clinically important in preventing pain and degenerative changes due to overstuffing. METHODS: Six human cadaveric elbows were prepared on a custom-designed apparatus simulating muscle loads and passive flexion from 0° to 90° under gravity valgus torque while measuring joint contact pressures in this biomechanical study. Each elbow was tested sequentially starting with the intact specimen followed by insertion of a radial head prosthesis with 0, +2, and +4 mm of radial neck height, respectively. RESULTS: Capitellar mean contact pressures significantly increased after insertion of +2 and +4 mm radial head prostheses (p < 0.03). The capitellar mean contact pressure with a 0 mm radial head prosthesis was 97 KPa. Insertion of +2 mm and +4 mm radial heads increased mean contact pressures to 391 KPa (p = 0.001) and 619 KPa (p = 0.001), respectively, with 90° of elbow flexion. DISCUSSION: Increasing radial prosthesis height by 2 mm significantly increases capitellar contact pressures and reduces coronoid contact pressures.

Replacing the cyano (-C[triple bond, length as m-dash]N) group to design environmentally friendly fused-ring electron acceptors.

The cyano-group (-C[triple bond, length as m-dash]N) is an electron-withdrawing group, which has been widely used to construct high-performance fused-ring electron acceptors (FREAs). Benefiting from these FREAs, the power conversion efficiency of organic solar cells has recently exceeded 18%. However, malononitrile is a highly toxic substance used to introduce -C[triple bond, length as m-dash]N during the synthesis of these FREAs. Therefore, the synthesis processes of most high-performance FREAs are typically harmful to the environment. Our previous work demonstrated that the electron-withdrawing ability of -C[triple bond, length as m-dash]N is necessary for FREAs. Thus, the use of other electron-withdrawing groups instead of -C[triple bond, length as m-dash]N to design environmentally friendly FREAs is feasible. We utilized seven electron-withdrawing groups, namely, -C[double bond, length as m-dash]NH, -N[double bond, length as m-dash]O, -CH[double bond, length as m-dash]O, -CO-CH3, -CO-OH, -CO-Cl, and -CO-Br, to replace -C[triple bond, length as m-dash]N in the commonly used acceptor Y6 to design new FREAs (Y6-CNH, Y6-NO, Y6-CHO, Y6-COCH3, Y6-COOH, Y6-COCl, and Y6-COBr). Multi-scale theoretical calculation methods were used to investigate the photoelectronic properties of these new FREAs, including energy level, absorption spectrum, exciton binding energy, and electron mobility. The results showed that Y6-CNH, Y6-COCH3 and Y6-COOH are unsuitable for use as acceptor materials because of their high frontier molecular orbital energy level and weak electron affinity. The strong absorption intensity and weak exciton binding energy of Y6-CHO, Y6-COCl, and Y6-COBr indicated that they can absorb more solar energy than Y6 and excitons are easier to separate into free charges. The electron mobility of Y6-CHO (3.53 × 10-4 cm2 V-1 s-1) was found to be approximately 28 times that of Y6-COCl (1.24 × 10-5 cm2 V-1 s-1) and Y6-COBr (1.28 × 10-5 cm2 V-1 s-1). The possible synthetic routes to Y6-CHO are environmentally friendly. Therefore, -CH[double bond, length as m-dash]O is the most suitable electron-withdrawing group for constructing high-performance environmentally friendly FREAs. This work can provide a new molecular design perspective in experimental science for developing high-performance environmentally friendly FREAs.

Atomic Bonding and Electronic Binding Energy of Two-Dimensional Bi/Li(110) Heterojunctions via BOLS-BB Model.

Combining the bond-order-length-strength (BOLS) and atomic bonding and electronic model (BB model) with density functional theory (DFT) calculations, we studied the atomic bonding and electronic binding energy behavior of Bi atoms adsorbed on the Li(110) surface. We found that the Bi atoms adsorbed on the Li(110) surface form two-dimensional (2D) geometric structures, including letter-, hexagon-, galaxy-, crown-, field-, and cobweb-shaped structures. Thus, we obtained the following quantitative information: (i) the field-shaped structure can be considered the bulk structure; (ii) the field-shaped structure of Bi atom formation has a 5d energy level of 22.727 eV, and in the letter shape structure, this energy is shifted to values greater than 0.342 eV; and (iii) the Bi/Li(110) heterojunction transfers charge from the inner Li atomic layer to the outermost Bi atomic layer. In addition, we analyzed the bonding and electronic dynamics involved in the formation of the Bi/Li(110) heterojunctions using residual density of states. This work provides a theoretical reference for the fine tuning of binding energies and chemical bonding at the interfaces of 2D metallic materials.

Intramolecular Charge Transfer-Based Conjugated Oligomer with Fluorescence, Efficient Photodynamics, and Photothermal Activities.

To develop efficient photoactive agents with satisfactory fluorescence, photodynamic, and photothermal effects is crucial for a phototherapeutic strategy to combat cancer diseases and pathogenic microbes. Herein, a water-soluble donor-acceptor-donor (D-A-D) structured conjugated oligomer was designed and synthesized, consisting of two cyclopenta-dithiophene (CDT) units as the electron donor and boron dipyrromethene (BODIPY) as the electron acceptor. Upon excitation, dual emission was observed for CDT-BODIPY with blue and red fluorescence peaks at 463 nm and at 730 nm, respectively, which was ascribed to intramolecular charge transfer (ICT). Due to the ICT effect, the singlet-to-triplet intersystem crossing rate of CDT-BODIPY was also enhanced, leading to an outstanding photodynamic behavior to produce reactive oxygen species (ROS). Meanwhile, its low bandgap also enabled it a moderate photothermal capability with a conversion efficiency of 33.1%. Taking advantage of its phototriggered activities, this conjugated oligomer exhibited an effective inhibition behavior on the pathogenic growth of Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Candida albicans (C. albicans), which can be guided by dual-wavelength fluorescence imaging. This D-A-D type conjugated oligomer with balanced photophysical characteristics provides a promising strategy to imaging-guided photoactive therapy.

Aqueous Systems with Tunable Fluorescence Including White-Light Emission for Anti-Counterfeiting Fluorescent Inks and Hydrogels.

White-light-emitting materials have attracted wide interest for potential applications in information displays and lighting. To date, the majority of reported white-light-emitting materials have been multicomponent systems that are typically processed with organic solvents. These features are associated with complex processing, poor white-light quality, and environmental pollution. Herein, a white-light-emitting aqueous system is realized by encapsulating a fluorophore, which has a vibration-induced emission effect, in Pluronic F127 micelles. Tunable multicolor fluorescence is achieved by changing the temperature, and the use of organic solvents is effectively avoided. Through this process, white-light emission with Commission Internationale de l'Eclairage coordinates of (0.3351, 0.3326) is obtained, which is very close to pure white light, and its color rendering index is as high as 89. The fluorescence color tunability of this system could be performed in a wide temperature range, rendering it a potential material in optical thermometry. Besides, the aqueous system also allows for the application of the material as a fluorescent ink and white-light-emitting hydrogels. Information could be embedded in paper-based materials and hydrogels through the fluorescence quenching effect of iron ions (Fe3+) on the fluorophore. Fluorescence could then be recovered upon removal of Fe3+ by adenosine 5'-triphosphate. Thus, fluorescent patterning and triple-mode anti-counterfeiting could be expected due to the temperature-sensitive emission, fluorescence quenching, and recovering properties.

Understanding atomic bonding and electronic distributions of a DNA molecule using DFT calculation and BOLS-BC model.

Deoxyribonucleic acid (DNA) is an important molecule that has been extensively researched, mainly due to its structure and function. Herein, we investigated the electronic behavior of the DNA molecule containing 1008 atoms using density functional theory. The bond-charge (BC) model shows the relationship between charge density and atomic strain. Besides, the model mentioned above is combined with the bond-order-length-strength (BOLS) notion to calculate the atomic cohesive energy, the bond energy, and the local bond strain of the DNA chain. Using the BOLS-BC model, we were able to obtain information on the bonding features of the DNA chain and better comprehend the associated properties of electrons in biological systems. Consequently, this report functions as a theoretical reference for the precise regulation of the electrons and the bonding states of biological systems.

Structure and Stability of Aromatic Nitrogen Heterocycles Used in the Field of Energetic Materials.

Understanding the stabilization of nitrogen heterocycles is critical in the field of energetic materials and calls for innovative knowledge of nitrogen aromatics. Herewith, we report for the first time that nitrogen lone pair electron (NLPE) delocalization in five-membered nitrogen heterocycles creates a second σ-aromaticity in addition to the prototypical π-aromaticity. The NLPE delocalization and the attendant dual-aromaticity are enhanced as more carbon atoms in the ring are substituted by unsaturated nitrogen atoms. The presence of adjacent nitrogen atoms in the ring can enhance the aromaticity of the nitrogen heterocycles and improve in-crystal intermolecular binding strength but will decrease the firmness of the individual molecular architecture. Notably, such σ-aromaticity is not present in six-membered nitrogen heterocycles, probably due to the longer bonds and broader regions of their rings; therefore, six-membered heterocycles present overall lower aromaticity than five-membered heterocycles. This work brings new knowledge to nitrogen aromatics and is expected to inspire broad interest in the chemistry community.

Functionalizing triptycene to create 3D high-performance non-fullerene acceptors.

Non-fullerene acceptors have been widely investigated for organic solar cells (OSCs). In particular, fused-ring electron acceptors (FREAs), composed of two strongly electron-withdrawing end groups connected by a planar fused-ring core, have been successfully applied to develop high-performance OSCs (>16%). In this work, we proposed two novel 3D FREAs named BFT-3D and BFTT-3D, which can reduce the formation of crystalline domains and increase the interface with donors to promote exciton separation. These 3D FREAs consist of three strongly electron-withdrawing end groups linked by a central triptycene hub to form a three-bladed propeller nanostructure. In comparison with high-performance FREA (ITOIC-2F), these FREAs have stronger absorption intensity and smaller exciton binding energy. These findings demonstrated that these three-bladed propeller-shaped FREAs can absorb abundant energy from sunlight to generate excitons, easily separate excitons to free electrons and holes, and reduce the recombination of excitons. In addition, the electron mobility of BFT-3D (8.4 × 10-4 cm2 V-1 s-1) is higher than that of BFTT-3D (1.0 × 10-4 cm2 V-1 s-1), which indicated that the appropriate 3D core structure was conducive to the electron mobility of the three-bladed propeller-shaped FREAs. It can effectively improve the current density to enhance the performance of OSCs. These findings will provide new perspectives for experimental scientists to synthesize high-performance FREAs.

Energetic Butterfly: Heat-Resistant Diaminodinitro trans-Bimane.

Due to a significant and prolific activity in the field of design and synthesis of new energetic molecules, it becomes increasingly difficult to introduce new explosophore structures with attractive properties. In this work, we synthesized a trans-bimane-based energetic material-3,7-diamino-2,6-dinitro-1H,5H-pyrazolo-[1,2-a]pyrazole-1,5-dione (4), the structure of which was comprehensively analyzed by a variety of advanced spectroscopic methods and by X-ray crystallo-graphy (with density of 1.845 g·cm-3 at 173 K). Although obtained crystals of 4 contained solvent molecules in their structure, state-of-the-art density functional theory (DFT) computational techniques allowed us to predict that solvent-free crystals of this explosive would preserve a similar tightly packed planar layered molecular arrangement, with the same number of molecules of 4 per unit cell, but with a smaller unit cell volume and therefore higher energy density. Explosive 4 was found to be heat resistant, with an onset decomposition temperature of 328.8 °C, and was calculated to exhibit velocity of detonation in a range of 6.88-7.14 km·s-1 and detonation pressure in the range of 19.14-22.04 GPa, using for comparison both HASEM and the EXPLO 5 software. Our results indicate that the trans-bimane explosophore could be a viable platform for the development of new thermostable energetic materials.

Surface-Engineered Gold Nanoclusters with Biological Assembly-Amplified Emission for Multimode Imaging.

Here, we develop bifunctional ligand-engineered gold nanoclusters (AuNCs) as signal amplifying reporters for multimode imaging. Modified streptavidin (SA) and biotin alkyl acid-based ligands were applied to AuNCs to form AuNC-SA and AuNC-biotin. The zwitterionic ligands promoted bioassembly and avoided nonspecific adsorption. The AuNCs resisted aggregation-induced quenching and showed strong emission benefited from biological self-assembly. The engineered AuNCs featured stable emission, a large two-photon absorption cross section, long fluorescence lifetime, and good biocompatibility. Thus, cell-expressed antigen-induced protein-binding events were effectively converted into signals from the biological assemble of AuNCs. We performed a comprehensive assay of specific antigens and the cell structure, through one-photon imaging, two-photon imaging, and fluorescence lifetime imaging of AuNCs in a simple, sensitive, and reliable way.

Mechanism and Functionality of Pnictogen Dual Aromaticity in Pentazolate Crystals.

Our recent work (J. Phys. Chem. Lett. 2019, 10, 2378) reported the discovery of the abnormal pnictogen dual aromaticity (π and σ) in cyclo-N5- , which makes the anion unstable in nature but confers enhanced stability in sufficiently acid solution. Herein, we present systematic quantum calculations on the structures, energetics and dynamics of the pentazolate salt and metal pentazolate hydrates, focusing on the mechanism and functionality of the pnictogen dual aromaticity in these crystals, which are verified by experiments. We find that owning a net charge of -e is crucial to the formation of the dual aromaticity and the stabilization of the cyclo-N5- . The competition between the dual aromaticity and the proton affinity drives the cyclo-N5- to be unreactive to acid and remain unprotonated in these crystals. We decompose the crystal packing effect into pure mechanical compression and interspecies nonbonding interactions, and figure out that the type and number of the adjacent counterions of the cyclo-N5- anion, instead of the compression effect, accounts for the protonation state reversion in the vacuum and in the crystal. The current work supports our original conclusion (Science 2018, 359, eaas8953) and is expected to provide compelling evidence against the current debate on the cyclo-N5- stability (Science 2018, 359, eaao3672; J. Phys. Chem. Lett. 2018, 9, 7137; J. Am. Chem. Soc. 2019, 141, 2984).