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The spin-crossover (SCO) can be triggered by light or pressure changes, making it a promising system for multifunctional switches and memory devices at the molecular level. In this work, we have reported a NIR-responsive spin state switching system via doping layered Co(pyridine) 2 Ni(CN) 4 (Co-MOF) into the stable polyvinylidene fluoride matrix for the first time. The layered Co-MOF has shown a rapid response of color change between gray-white and blue, which could be attributed to the SCO behavior triggered by NIR illumination. The new system ensures the soft network structures of the matrix to facilitate the homogeneous distribution of layered Co-MOF, both of which contribute to outstanding reversibility performance, including fast response, coloration in a short period, and decoloration in the ambient environment. This work provides a viable strategy to construct a new NIR-triggered SCO system for molecular switches and spintronic devices. • A NIR-responsive spin state switching system was successfully constructed. • A rapid response of color change between gray-white and blue has been triggered by NIR illumination. • Outstanding reversibility and stability performance has been demonstrated. [ABSTRACT FROM AUTHOR]

The crystals of two organic salts of tris(hydroxymethyl)aminomethane (THAM) with p-hydroxybenzoic acid (PHBA) and salicylic acid (SA) were obtained. Their crystal structures were characterized by single-crystal X-ray diffraction, IR spectra, differential scanning calorimetry, thermogravimetric analyses and hot stage microscopy. Wherein, 1 forms a 1:1 (THAM:PHBA) salt, and 2 forms a 2:2:1 (THAM:SA:HO) salt. The structure determination shows that the two salts are all primarily stabilized by strong O···H hydrogen bonds interaction between THAM and the two acids. The Hirshfeld surfaces and fingerprint plots of the reported salts were prepared and analyzed and reveal that the structures are stabilized by O···H, H···H, C···H, O···O and O···C intermolecular interactions. Graphical Abstract: The paper is about synthesis, crystal structure, thermal and Hirshfeld surfaces analysis of two THAM salts.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

• Establishing a set of models of supramolecular complexes to further study substituent effect on the formation process of co-crystals. • Providing a widely applicable method for modifying industrial raw materials, finished products and auxiliary products. • Co-crystal strategy has been proven to be effective in the field of Spice Modification, improving the stability and release characteristics of traditional flavoring agents. Co-crystallizations of 2,3,5,6-tetramethyl pyrazin (TMP) with different substituted aromatic compounds [3,5-dinitrosalicylic acid (DNS), 5-chlorosalicylic acid (CSA) and 3,5-dichlorosalicylic acid (DCA)] have been performed, resulting in the formation of three co-crystals (TMP : DNS = 1:1 for 1 ; TMP : CSA = 1:2 for 2 ; TMP : DCA = 1:2 for 3). Those newly co-crystals were characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analyses (TGA), UV–Vis spectroscopy and X-ray diffraction (XRD). The Hirshfeld surface analysis revealed that N–H∙∙∙O/O–H∙∙∙N strong hydrogen bonds and other intermolecular interactions such as H∙∙∙H, C–H∙∙∙π, π∙∙∙π and lone-pair∙∙∙π participated in a cooperative way to stabilize the supramolecular structures. Additionally, thermodynamic results indicated that the halogen bonding exerted a positive effect on the stability of co-crystal structures, further improving the release process of pyrazine spices. This work provided a co-crystal strategy for the solidification of liquid pyrazine-related spices for broader applications. [Display omitted] [ABSTRACT FROM AUTHOR]

Developing versatile printing inks with good biocompatibility is essential for the fabrication of functional colored contact lenses. In this work, by employing a new kind of printing ink that shows humidity-induced discoloration, multifunctional colored contact lenses have been constructed. The obtained products have displayed distinct and stable all-weather humidity-triggered discoloration under ambient conditions. More importantly, combined with a smartphone, the quantitative and qualitative relationship between the discoloration of colored contact lenses and environmental humidity has been established, which is expected to realize the early prediction of humidity-related eye diseases in a portable, economical, and in-situ manner. • A new kind of printing ink that shows humidity-induced discoloration has been prepared. • The colored contact lens with all-weather humidity-triggered discoloration has been constructed. • The quantitative and qualitative relationship between the discoloration of colored contact lenses and environmental humidity has been established. [ABSTRACT FROM AUTHOR]

• Efficient mercury capture by ultrathin 2D nanosheets has been presented. • Highly uptake capacity and extremely fast kinetics have been observed. • Practically applicable recycling ability have been demonstrated. • The challenging goal of "turning waste into treasure" has been achieved. The retrieval of toxic heavy metals ions from aqueous resources effectively and facilely, by using low-cost, robust, and efficient technologies, is imperative and of significant environmental and societal importance. Adding on, the comprehensive utilization of the captured heavy metals remains a huge challenge. Herein, we demonstrate that the single-layered sulfur-rich two-dimensional (2D) metal-organic frameworks (MOFs) nanosheets 2D-NCS ({[Co(NCS) 2 (pyz) 2 ]} n) (pyz = pyrazine), which featured with the merits of ultrahigh sulfur content (19.1%), tremendous affinity of thiocyanate group, and fully accessible chelating sites arrayed on the double surfaces of the nanosheets, serving as an ideal adsorbent materials for mercury chloride capture from aqueous solution, with considerable capacity, efficiency, effectivity and recycling ability. The maximum uptake capacity is found to be 1698 mg g−1, accompanied by high affinity (K d value of 2.26 × 106 mL g−1) and extremely fast kinetics (reduce the mercury concentration from 10 ppm to 1 ppb within 15 min). More importantly, 2D-NCS can act as versatile building blocks for the construction of solid three-dimensional porous architecture 2D-NCS@Hg , achieving the challenging goal of "turning waste into treasure". These results have demonstrated the enormous potential of ultrathin 2D MOFs nanosheets for high-performance environmental remediation. [ABSTRACT FROM AUTHOR]

Abstract A new complex [Fe(CN) 2 (bipy-NH 2) 2 ] (2 , bipy-NH 2 = 4, 4′-diamino-2, 2′-bipyridine), which was designed through ligand exchange strategy, has been prepared and characterized. The magnetism properties of 2 have been tuned through protonate the amino groups on bipy-NH 2 ligand with HCl in stoichiometric ratio 2 :HCl below 1:1. Further increase the ratio exceed 1:1 has induced the distortion of the bipy-ammonium moieties in bipy-NH 3 2+ cation, with the dihedral angle involving the mean plane change from 0° to 37°. This distortion, on the one hand, responsible for the decomposition of 2 , on the other hand, take charge the break of the precursor complex 1 ([Fe(H 2 Bpz 2) 2 (bipy-NH 2)]) (pz = pyrazolyl) upon protonation. Graphical abstract Tuning the magnetism properties of a new complex [Fe(CN) 2 (bipy-NH 2) 2 ] (2) through protonation of the ligand bipy-NH 2 with HCl have been investigated with stoichiometric ratio of 2 :HCl below 1:1. While once the ratio larger than 1:1, ligand bipy-NH 2 has distorted with the mean plane of bipy-ammonium moieties to form a dihedral angle large to be 37°. Unlabelled Image Highlights • The protonation of a Fe(II) complex has been investigated. • The mechanism of protonation induced decomposition of Fe(II) complex has been proposed. • The mean plane of bipy-ammonium moieties has been distorted with dihedral angle large to be 37°. [ABSTRACT FROM AUTHOR]

A new complex of the title system ([2(H 3 O + )·18-crown-6]·2[BF 4 − ]), which was induced by external magnetic field, has been prepared and characterized. When compared with other two members of the same system, the proton transfer induced by magnetic field from HBF 4 to H 2 O has leads to the co-plane of six oxygen atoms in the crown and stronger H F and O F intermolecular interactions, which can be attributed to the closer contacts between 18-crown-6, oxonium ion H 3 O + and counterion BF 4 − . In addition, a compression effect of crystals stacking has been observed. These results are of importance for the evaluation the effect of magnetic field on the host–guest systems. [ABSTRACT FROM AUTHOR]

In this work, two new single crystals of copper-tetraphenylporphine (Cu-TPP) (crystals 2 and 3), which were induced by external magnetic fields with strengths of 0.5 and 0.8 T, respectively, have been prepared and characterized by single-crystal X-ray diffraction and Hirshfeld surface analysis. Compared with the original Cu-TPP (crystal 1), crystals 2 and 3 exhibit significant differences in their unit cell parameters, crystalline stacking styles and intermolecular interactions, resulting in a “compressed” crystal packing. Here, the number of closer interactions (H…H, C…H/H…C) increased with the magnetic field strength, accompanied by a decrease in the number of π…π (C…C) interactions as a sacrifice. On considering the results of our previous work, the results here suggest that a magnetic field has a different influence on the crystallization process of mono-component and multi-component materials, which will certainly provide some suggestions for the design of crystallization strategies for other materials with the presence of an external magnetic field. [ABSTRACT FROM AUTHOR]

Two zinc (II) pseudo-halide complexes [Zn( L 1 )(N 3 ) 2 ] n ( 1 L 1 : 1,2-diaminocyclohexane) and Zn( L 2 ) 2 (N 3 ) 2 ( 2 L 2 : 4,5-dimethy-2-(pyridine-2-yl) imidazole) have been synthesized and characterized. Single-crystal X-ray structural analysis revealed that the central Zn II atoms in 1 displays distorted trigonal bipyramidal arrangement with a 1D chain structure bridged by N 3 − anions, while in 2 , the central Zn II atoms incorporating with two bidentate L 2 ligands, and adopts an octahedral geometry and shows a “butterfly” coordination framework. Structural analysis demonstrated that the organic ligands play an important role in determining the resultant structure. In addition, both complexes were further characterized by thermal stability properties and Hirshfeld surface analysis. [ABSTRACT FROM AUTHOR]

An investigation into the effect of switching methoxy and hydroxyl groups on molecular salts is presented in this study. The salts HL1+·NO3− (1), L1·HL1+·ClO4− (2), L1·HL1+·H2PO4−·H2O (3), HL2+·NO3− (4), HL2+·ClO4− (5) and HL2+·H2PO4− (6) were synthesized and structurally characterized. The study was carried out by analyzing the crystal structure, properties and intermolecular interactions within each of the salts using IR and fluorescence spectra, TGA, Hirshfeld surface analyses and π…π stacking motifs. Salt 1 has a layered structure, while 4 has a distorted 3-D structure. Salt 2 possesses an edge-to-face type plane interaction, while 5 is formed with a twisted structure. It is important to note that water molecules play a key role in the 1-D chain structure of salt 3. The π…π stacking motif of salts 1–3 have a herringbone structure, while salts 3–6 exhibit a γ-structure. In addition, the competitive crystallization of the synthetic salts was investigated and found to be consistent with the measured solubility. [ABSTRACT FROM AUTHOR]

By using the ligands 4-(4-bromobenzylideneamino)-4H-1,2,4-triazole (L1) and 4-(4-iodobenzylideneamino)-4H-1,2,4-triazole (L2), four different organic salts HL1+·Cl− (1), L1·HL1+·ClO4− (2), HL2+·Cl− (3), and L2·HL2+·ClO4− (4) have been synthesized and structurally characterized through single-crystal X-ray diffraction (L1, L2, 2 and 3) and PXRD (1 and 4) measurements. The results revealed that ligands L1 and L2 themselves exhibit a polymeric 1-D chain in a zigzag structure connected by C–Br…N and C–I…N halogen-bonding contacts, respectively. L1 in salt 2 was connected into a 3-D structure through N–H…O hydrogen-bonding contacts, while the interleaved 3-D network of L2 in salt 3 was mainly connected by C–I…Cl halogen-bonding contacts. As a result, the fluorescence properties of ligands L1 and L2 were reserved in halogen-bonding connected salts 1 and 3, while there was a reduction in hydrogen-bonding connected salts 2 and 4. Thus, the relationship between emission properties and halogen-bonding contacts can be proposed. [ABSTRACT FROM AUTHOR]

Fluorescent materials have many interesting applications, but it remains difficult to control the luminescence of organic materials and in particular to retain the same luminescence in solution and in the solid state, a property of interest for various imaging applications. In this work, the influence of inorganic-anions on the crystal structure and physical–chemical properties of a series organic salts L + Cl − ( 1 ), L + ClO 4 − ( 2 ), L + NO 3 − ·H 2 O ( 3 ), 2 L + SO 4 2− ·2H 2 O ( 4 ) ( L = 4-[(4H-1,2,4-triazol-4-ylimino)methyl]phenol) has been investigated. Single crystal X-ray analyzes revealed that salt 1 formed a linear structure connected by H⋯O interactions, while salts 2 – 4 all formed 2D network structures through O⋯O interactions. The protonated L + s adopt face-to-face slipped π-stacked arrangement in salts 1 and 3 , while display monomer arrangements in 2 and 4 , the latter can be attribute to the entrapment of heavy anions in the crystal lattices. Optical-properties measurements of these four salts have shown L + arrangements dependent on solid-state properties: salt 1 and 3 show broad emission bands ( λ 1 = 478 nm, λ 2 = 487 nm) with a red shift of about 60 nm relative to its fluorescence in solvents, while 2 and 4 are similar to each other, exhibiting sharp bands ( λ 3 = 453 nm, λ 2 = 433 nm) with the higher ϕ PL values ( ϕ PL1 = 0.08, ϕ PL1 = 0.15, ϕ PL1 = 0.06, ϕ PL1 = 0.14). These results demonstrated the significant influence of inorganic-anions on the organic salts and the optical properties of organic materials could be modulated by entrapping different anions in lattice. [ABSTRACT FROM AUTHOR]

In the present study, the assembly of 6-aminonicotinic acid with inorganic acids (HBr, HNO 3 and H 3 PO 4 ) has been performed, which resulted in the molecular salts C 6 H 7 N 2 O 2 + ·Br − ( 1 ), C 6 H 7 N 2 O 2 + ·NO 3 − ( 2 ) and C 6 H 7 N 2 O 2 + ·H 2 PO 4 − ( 3 ), respectively. These three molecular salts have been characterized by single-crystal X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetric analyses (TGA) and UV–Vis absorption spectroscopy (UV). The results revealed that molecular salt 1 exhibits an infinite 1-D chain structure stabilized mainly by N–H⋯Br contacts, while 2 and 3 show a 2-D network and a 3-D stereoscopic framework, respectively, which are stabilized mainly by strong N–H⋯O hydrogen bonding contacts. Hirshfeld surface analysis demonstrated the presence of H⋯H, O–H⋯N, C–H⋯π and π⋯π intermolecular interactions. In addition, the UV–Vis spectra exhibit a slight blue-shift to a shorter wavelength, which suggests the clear influence of the inorganic anions. [ABSTRACT FROM AUTHOR]

The co-crystallization of a benzimidazole derivative ( 1, CHNO, 3-[[[2-[[(4-Cyanophenyl) amino]methyl]-1-methyl-1H-benzimidazol-5-yl]carbonyl]pyridin-2-ylamino]propionic acid ethyl ester), with fumaric acid (FA) and maleic acid (MA), has been performed. The FA and MA molecules, both are connected with two molecules of CHNO, giving birth to a three-components compound ( 1·0.5FA, CHNO) and a four-components compound ( 1·MA, CHNO). Single-crystal X-ray diffractions show that the three different planar moieties (4-cyanophenyl, benzimidazol, and pyridin-2-yl) in compound CHNO display ' cis-form' conformation ( a) in the crystal of 1, while exhibiting 'intermediate-state' conformation ( b) and ' trans-form' conformation ( c) in compounds 1·0.5FA and 1·MA, respectively. Hirshfeld surfaces analysis, DFT calculations, DSC measurements, IR and Raman spectroscopy were performed, which revealed that the thermal stability of the three conformations follows the order c > b > a. [ABSTRACT FROM AUTHOR]

Four new complexes, [Co(dmbpy) 2 (dca) 2 ]·CH 3 OH ( 1 ), [Ni(dmbpy) 2 (dca) 2 ]·CH 3 OH ( 2 ), [Zn(dmbpy) 2 (dca) 2 ]·( 3 ) and [Cu(dmbpy) 2 (OH) 2 ]·5H 2 O ( 4 ) (dca = dicyanamide), derived from 4,4′-dimethyl-2,2′-bipyridine (dmbpy) have been synthesized and characterized by elemental analysis, TGA and single-crystal X-ray diffraction. Crystal structures and Hirshfeld surfaces analysis revealed that the complexes 1 – 3 were mainly supported by O H ⋯ N, C H ⋯ N and π ⋯ π intermolecular interactions, and for complex 4 , the uncoordinated water molecules play a key role in the construction of the 3D stacking motif. UV spectrum measurements demonstrate that all of the complexes show typical metal to ligand charge transfer (MLCT) absorption bands between 301 and 306 nm. Moreover, after complexation, the absorption maximum bands about intraligand π → π* transitions similarly show slightly red shift compared to dmbpy ligand, consisting with the DFT calculations. [ABSTRACT FROM AUTHOR]

Single crystals of compound L (CHN): 4-(2-benzimidazole)-1,2,4-triazole and its hydrate were obtained via slow evaporation. The structures of the crystals were characterized by IR, TGA/DSC and X-ray diffraction analysis. Molecules in crystal 1 are linked by a combination of N-H···N and C-H···N hydrogen bonds into 2D layers, and further stacked into a 3D structure by π··· π stacking interactions. Compared to crystal 1, the water molecules play a key role in the construction of the crystal structure of hydrate 2. The 2D layers were formed via O-H···N, O-H···O, N-H···N hydrogen bonds, and further stacked by O-H···O hydrogen bonds and π··· π stacking interactions in crystal 2. A detailed analysis of the intermolecular interactions and crystal packing via Hirshfeld surface analysis and fingerprint plots reveals that the structures are stabilized mainly by N···H/H···N, C···H/H···C hydrogen bonds, H···H weak interactions and π··· π stacking interactions. [ABSTRACT FROM AUTHOR]

2,3-Dimethylpyrazine and 1,2-bis(4-pyridyl)ethane are both N-containing aromatic heterocyclics with two N atoms approximately in the para position. We here report two compounds derived from these heterocyclics (compounds 1 and 2). Compounds 1 and 2 both form a 1:1 2,3-dimethylpyrazine:perchloric acid (PA) and 1,2-bis(4-pyridyl)ethane:PA cocrystal, respectively. Their crystal structures were characterized by single-crystal X-ray diffraction, which revealed that the C-H⋯O and N-H⋯O hydrogen bonding interactions were found to stabilize the crystal structure in compounds 1 and 2. However, PA plays a necessary role for the one-dimensional structure in 1 and the three-dimensional structure in 2. Hirshfeld surfaces and fingerprint plots were applied to get the same conclusion. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) MOFs nanosheets are prosperous regarding the novel peculiarity of nano-interface and broad development prospects, but the key to achieving the control and design of 2D nanomaterials' morphology is still arduous. In this work, we prepared two complexes contained pyrazine ligand, namely Ni(pyz) 2 Cl 2 and Ni(pyz) 2 Br 2 (pyz = pyrazine), which derived from a synthesis of bridged pyrazine and nickel halogen nide. 2D nanomaterials of them were obtained by using the liquid phase exfoliation method to feature a series of structure and surface morphology. We investigated the difference in physical and chemical properties between 2D MOFs nanomaterials and bulk materials, and studied the influence of different halogen interactions on the morphology of nanomaterials. The results showed that the stacking force and electronic transition have made a significant influence on the 2D nanomaterials. [Display omitted] • Ultra-thin 2D nanosheets of Ni-based MOFs have been prepared. • The correlation between halogen interactions and morphologies of 2D nanosheets has been proposed. • The influence of halogen interactions on the properties of 2D nanosheets has been demonstrated. [ABSTRACT FROM AUTHOR]