A Hydrogen Bonded Supramolecular Framework Birefringent Crystal

Birefringent crystals could modulate the polarization of light and are widely used as polarizers, waveplates, optical isolators, etc. To date, commercial birefringent crystals have been exclusively limited to purely inorganic compounds such as α-BaB₂O₄ with birefringence of about 0.12. Herein, we report a new hydrogen bonded supramolecular framework, namely, Cd(H₂C₆N₇O₃)₂⋅8 H₂O, which exhibits exceptionally large birefringence up to about 0.60. To the best of our knowledge, the birefringence of Cd(H₂C₆N₇O₃)₂⋅8 H₂O is significantly larger than those of all commercial birefringent crystals and is the largest among hydrogen bonded supramolecular framework crystals. First-principles calculations and structural analyses reveal that the exceptional birefringence is mainly ascribed to strong covalent interactions within (H₂C₆N₇O₃)⁻ organic ligands and the perfect coplanarity between them. Given the rich structural diversity and tunability, hydrogen bonded supramolecular frameworks would offer unprecedented opportunities beyond the traditional purely inorganic oxides for birefringent crystals.     

A Humidity-Induced Large Electronic Conductivity Change of 107 on a Metal-Organic Framework for Highly Sensitive Water Detection

The electronic conductivity (EC) of metal–organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H₂O on the EC of MOFs is rarely reported. We explored the effect of H₂O on the EC in the MOFs (NH₂)₂-MIL-125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 10⁷ on H₂SO₄@(NH₂)₂-MIL-125 by H₂O was observed. Brønsted acid–base pairs formed with the −NH₂ groups, and H₂SO₄ played an important role in promoting the charge transfer from H₂O to the MOF. Based on H₂SO₄@(NH₂)₂-MIL-125, a high-performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H₂O can remarkably influence the EC of MOFs, but it also revealed that post-modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high-performance sensing materials.     

Hybrid Double Perovskite Derived Halides Based on Bi and Alkali Metals (K,Rb): Diverse Structures,Tunable Optical Properties and Second Harmonic Generation Responses

Double perovskites (DP) have attracted extensive attention due to their rich structures and wide application prospects in the field of optoelectronics. Here, we report 15 new Bi-based double perovskite derived halides with the general formula of A₂BBiX₆ (A=organic cationic ligand, B=K or Rb, X=Br or I). These materials are synthesized using organic ligands to coordinate with metal ions with a sp³ oxygen, and diverse structure types have been obtained with distinct dimensionalities and connectivity modes. The optical band gaps of these phases can be tuned by changing the halide, the organic ligand and the alkali metal, varying from 2.0 to 2.9 eV. The bromide phases exhibit increasing photoluminescence (PL) intensity with decreasing temperature, while the PL intensity of iodide phases changes nonmonotonically with temperature. Because the majority of these phases are non-centrosymmetric, second harmonic generation (SHG) responses are also measured for selected non-centrosymmetric materials, showing different particle-size-dependent trends. Our findings give rise to a series of new structural types to the DP family, and provide a powerful synthetic handle for symmetry breaking.     

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6H5)4P]2SbCl5 Enabled by Pressure-Induced Lone Pair-π Interaction

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C₆H₅)₄P]₂SbCl₅. In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb³⁺ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected “bridge” for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic–inorganic hybrid systems.     

Optimizing Acetylene Sorption through Induced-fit Transformations in a Chemically Stable Microporous Framework

Developing practical storage technologies for acetylene (C₂H₂) is important but challenging because C₂H₂ is useful but explosive. Here, a novel metal–organic framework (MOF) ( FJI-H36 ) with adaptive channels was prepared. It can effectively capture C₂H₂ (159.9 cm³ cm⁻³) at 1 atm and 298 K, possessing a record-high storage density (561 g L⁻¹) but a very low adsorption enthalpy (28 kJ mol⁻¹) among all the reported MOFs. Structural analyses show that such excellent adsorption performance comes from the synergism of active sites, flexible framework, and matched pores; where the adsorbed-C₂H₂ can drive FJI-H36 to undergo induced-fit transformations step by step, including deformation/reconstruction of channels, contraction of pores, and transformation of active sites, finally leading to dense packing of C₂H₂. Moreover, FJI-H36 has excellent chemical stability and recyclability, and can be prepared on a large scale, enabling it as a practical adsorbent for C₂H₂. This will provide a useful strategy for developing practical and efficient adsorbents for C₂H₂ storage.     

Targeted Synthesis of Isomeric Naphthalene-Based 2D Kagome Covalent Organic Frameworks

Targeted synthesis of kagome ( kgm ) topologic 2D covalent organic frameworks remains challenging, presumably due to the severe dependence on building units and synthetic conditions. Herein, two isomeric “two-in-one” monomers with different lengths of substituted arms based on naphthalene core (p-Naph and m-Naph) are elaborately designed and utilized for the defined synthesis of isomeric kgm Naph-COFs. The two isomeric frameworks exhibit splendid crystallinity and showcase the same chemical composition and topologic structure with, however, different pore channels. Interestingly, C₆₀ is able to uniformly be encapsulated into the triangle channels of m-Naph-COF via in situ incorporation method, while not the isomeric p-Naph-COF, likely due to the different pore structures of the two isomeric COFs. The resulting stable C₆₀@m-Naph-COF composite exhibits much higher photoconductivity than the m-Naph-COF owing to charge transfer between the conjugated skeletons and C₆₀ guests.     

Pseudo-2D Layered Organic-Inorganic Manganese Bromide with a Near-Unity Photoluminescence Quantum Yield for White Light-Emitting Diode and X-Ray Scintillator

Eco-friendly lead-free organic–inorganic manganese halides (OIMHs) have attracted considerable attention in various optoelectronic applications because of their superior optical properties and flexible solution processibility. Herein, we report a novel pseudo-2D layered OIMH (MTP)₂MnBr₄ (MTP: methyltriphenylphosphonium), which exhibits intense green emission under UV/blue or X-ray excitation, with a near-unity photoluminescence quantum yield, high resistance to thermal quenching (I_{150 °C}=84.1 %) and good photochemical stability. These features enable (MTP)₂MnBr₄ as an efficient green phosphor for blue-converted white light-emitting diodes, demonstrating a commercial-level luminous efficiency of 101 lm W⁻¹ and a wide color gamut of 116 % NTSC. Moreover, these (MTP)₂MnBr₄ crystals showcase outstanding X-ray scintillation properties, delivering a light yield of 67000 photon MeV⁻¹, a detection limit of 82.4 nGy s⁻¹, and a competitive spatial resolution of 6.2 lp mm⁻¹ for X-ray imaging. This work presents a new avenue for the exploration of eco-friendly luminescent OIMHs towards multifunctional light-emitting applications.     

Selective Encapsulation and Chiral Induction of C60 and C70 Fullerenes by Axially Chiral Porous Aromatic Cages

Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host–guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R- PAC-2 , S- PAC-2 (with Br substituents) and R- PAC-3 , S- PAC-3 (with CH₃ substituents) enantiomers. PAC-2 , rather than PAC-3 , achieves fullerene encapsulation and selective binding of C₇₀ over C₆₀ in fullerene carbon soot. More significantly, the occurrence of chiral induction between R- PAC-2 , S- PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C₇₀ selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.     

Facile Synthesis of Metallosalphen-Based 2D Conductive Metal-Organic Frameworks for NO2 Sensing: Metal Coordination Induced Planarization

As an emerging class of promising porous materials, the development of two-dimensional conductive metal organic frameworks (2D c-MOFs) is hampered by the few categories and tedious synthesis of the specific ligands. Herein, we developed a nonplanar hexahydroxyl-functionalized Salphen ligand (6OH-Salphen) through a facile two-step synthesis, which was further applied to construct layered 2D c-MOFs through in situ one pot synthesis based on the synergistic metal binding effect of the N₂O₂ pocket of Salphen. Interestingly, the C_2v-symmetry of ligand endows Cu-Salphen-MOF with periodically heterogeneous pore structures. Benefitting from the higher metal density and shorter in-plane metal-metal distance, Cu-Salphen-MOF showcased excellent NO₂ sensing performance with good sensitivity, selectivity and reversibility. The current work opens up a new avenue to construct 2D c-MOF directly from nonplanar ligands, which greatly simplifies the synthesis and provides new possibilities for preparing different topological 2D c-MOF based functional materials.     

Influence of Changing the Remote Substituents on Charge Transfer Properties of Cyanide-Bridged Trinuclear Fe−Ru−Fe Complexes

To investigate the effect of ligand remote (>10 Å) substituents on the bridging metal center on the metal-to-metal charge transfer (MMCT) properties in cyanidometa-bridged complexes, a series of new cyanidometal-bridged complexes and their one-electron and two-electron oxidation products have been synthesized and well characterized (namely, trans-[Cp(dppe)Fe−NC−(L)Ru(PPh₃)−CN−Fe(dppe)Cp][PF₆]_n (n=2, 3, 4) (L=dmptpy, 1[PF₆]_n ; L=meoptpy, 2[PF₆]_n ; L=t-Buptpy, 3[PF₆]_n ) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, PPh₃=triphenylphosphine, dmptpy=4′-(4-dimethylaminophenyl)-2,2′,6′,2′′-terpyridine, meoptpy=4′-(4-methoxyphenyl)-2,2′,6′,2′′-terpyridine, t-Buptpy=4′-(4-tertbutylphenyl)-2,2′,6′,2′′-terpyridine)). The investigations suggest that the cyanido-stretching (ν_CN) vibration energy for the complexes is unsensitive to the electron-donating ability change of the remote substituents of the cyanidometal bridging auxiliary ligand from tertbutyl, methoxy to dimethylamino group. However, the MMCT energies of the one- and two-electron oxidation complexes are still sensitive to the remote substituents of the ligand on the bridging metal center, and decreases with the increase of the electron-donating ability of the remote substituents from tertbutyl, methoxy to dimethylamino group. All one-electron and two-electron oxidation products belong to Class II mixed valence compounds according to the classification of Robin and Day.