Discrimination of Various Amine Vapors by a Triemissive Metal-Organic Framework Composite via the Combination of a Three-Dimensional Ratiometric Approach and a Confinement-Induced Enhancement Effect.

Multiemissive sensors are being actively pursued, because of their ratiometric luminescent detection capabilities, which demonstrates better sensitivity and selectivity than conventional single-emission sensors. Herein, we present a trichromatic white-light-emitting metal-organic framework (MOF) composite (Z3) by simultaneously incorporating red/green-emitting Pt/Ru complex cations into porous blue-emitting bio-MOF-1 through post-synthetic modification. With the help of a three-dimensional (3-D) dual-ratiometric luminescence recognition method, and unique turn-on responses of the red emission toward amine compounds (ACs), including NH3 and aliphatic amines, via confinement-induced luminescence enhancement effect, Z3 can work as a dual-ratiometric luminescent sensor for discrimination of 7 out of 11 AC vapors. This work not only provides a new AC sensing mechanism (confinement effect) that can induce a "turn-on" response but also proves that the accuracy and selectivity of composite sensor can be greatly improved through the combination of 3-D recognition method and the confinement effect. Thus, it open up fresh opportunities to develop composite sensors with excellent sensing and differentiating ability.

Effect of Intermolecular Interactions on Metal-to-Metal Charge Transfer: A Combined Experimental and Theoretical Investigation.

Understanding the effects of intermolecular interactions on metal-to-metal charge transfer (MMCT) is crucial to develop molecular devices by grafting MMCT-based molecular arrays. Herein, we report a series of solvent-free {Fe2 Co2 } compounds sharing the same cationic tetranuclear {[Fe(PzTp)(CN)3 ]2 [Co(dpq)2 ]2 }2+ (PzTp- =tetrakis(pyrazolyl)borate, dpq=dipyrido[3,2-d:2',3'-f]quinoxaline) square units but having anions with different size, including BF4 - , PF6 - , OTf- , and [Fe(PzTp)(CN)3 ]- . Intermolecular π⋅⋅⋅π interactions between dpq ligands, which coordinate to cobalt ions in the {[Fe(PzTp)(CN)3 ]2 [Co(dpq)2 ]2 }2+ units, can be modulated by introducing different counterions, regulating the distortion of the CoN6 octahedron and ligand field around the cobalt ions. This change results in different MMCT behavior. Computational analyzes reveal the substantial role of the intermolecular interactions tuned by the presence of different counteranions on the MMCT behavior.

Fluorescent Recognition of 4-Amino-2,6-dinitrotoluene by a Cerium-Based Metal-Organic Tetrahedron.

A cerium-based metal-organic tetrahedron has been developed as a highly selective and sensitive fluorescence sensor for the recognition of 4-amino-2,6-dinitrotoluene (4-ADNT). The redox-active tetrahedron could encapsulate 4-ADNT through weak interaction and spatial stereoselectivity, resulting in an enhanced fluorescence. The tetrahedral sensor Ce-ZPS is capable of realizing fluorescent sensing in urine and in cells and thus has the potential to detect 4-ADNT in organisms.

Simultaneous Modulation of Magnetic and Dielectric Transition via Spin-Crossover-Tuned Spin Arrangement and Charge Distribution.

Magnetic and dielectric properties have been tuned simultaneously by external stimuli with rapid and sensitive response, which is crucial to monitor the magnetic state via capacitive measurement. Herein, positive charged FeII ions were linked via negative charged [(Tp)FeIII (CN)3 ]- (Tp=hydrotris(pyrazolyl)borate) units to form a neutral chain. The spin-crossover (SCO) on FeII sites could be sensitively triggered via thermal treatment, light irradiation, and pressure. SCO switched the spin state of the FeII ions and antiferromagnetic interactions between FeIII and FeII ions, resulting in significant change in magnetization. Moreover, SCO induced rotation of negative charged [(Tp)FeIII (CN)3 ]- units, generating dielectric anomaly due to geometric change of charges distribution. This work provides a rational way to manipulate simultaneous variations in magnetic and dielectric properties utilizing SCO as an actuator to tune spin arrangement, magnetic coupling, and charge distribution.

Fluorescence modulation via photoinduced spin crossover switched energy transfer from fluorophores to FeII ions.

Molecular materials possessing phototunable fluorescence properties have attracted great interest owing to their potential applications in optical switches and storage. However, most fluorescence modulation is realized through light-responsive structural isomerization in solution. It is a formidable challenge to achieve phototunable fluorescence emission with high fatigue resistance and a fast response rate in the solid state for the development of devices. Here, a mononuclear compound was constructed via the coordination of fluorophores with FeII ions, whose electronic configuration changed from low spin to high spin upon light irradiation. The photoinduced spin crossover of FeII ions was accompanied by a 20% increase in the fluorescence emission intensity. A temperature-dependent spectroscopic study together with time-dependent density functional theory calculations revealed that the effective spectral overlap between the emission of the fluorophores and the absorption band of the FeII ions differed between the low spin and high spin states. The photoinduced spin crossover switched the energy transfer from the fluorophore to the FeII ion, resulting in fluorescence modulation. The presented results provide a novel approach for developing optical memory and sensors via electron rearrangement of photoinduced spin crossover.

A trichromatic MOF composite for multidimensional ratiometric luminescent sensing.

Low-cost, high-performance luminescent probes with wide application potential have been actively pursued. Conventional luminescent probes, which rely on single or dual emissions responsive to analyte molecules, demonstrate limited sensitivity and selectivity because the single emissions can be easily affected by many non-analyte factors, while the dual emissions can only offer single-ratiometric luminescent sensing. Here we report a white-light-emitting trichromatic MOF composite (W2) as the first multidimensional ratiometric luminescent probe. It is facilely synthesized by simultaneously incorporating red- and green-emitting iridium and ruthenium complex cations as encapsulated luminescent modules (ELMs) into a porous blue-emitting MOF via ion exchange. Specific volatile organic solvents (VOSs) can cause VOS-dependent changes to the MOF-to-ELM energy transfer efficiencies in W2, while nitroaromatic (NAC) vapors intriguingly and unprecedentedly quench the three emissions at different rates, both of which enable visible luminescent sensing. Each VOS can be correlated to a unique combination of the two MOF-to-ELM ratios of emission-peak heights, enabling a two-dimensional (2D) code recognition. Furthermore, the time-dependent evolution of the two ratios upon exposure to selective NAC vapors can be mapped out, achieving the first 3D code recognition. Both the synthetic and sensing strategies can be further implemented to develop low-cost and effective luminescent probes.

Two-dimensional nickel hydroxide/sulfides nanosheet as an efficient cocatalyst for photocatalytic H2 evolution over CdS nanospheres.

The intriguing features of two-dimensional (2D) materials such as better charge carrier separation and abundant surface reaction sites endow them with potential applications as cocatalysts in photocatalysis. In this paper, a ternary 2D nickel hydroxide/sulfides nanosheet composed of Ni(OH)2, Ni3S2 and NixS6 was loaded on CdS nanospheres by a simple chemical deposition route. The composition of nickel hydroxide/sulfides was determined clearly through an overall analysis using X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Mott-Schottky, electrochemical impedance, steady-state and time-resolved photoluminescence spectroscopy were used to investigate the charge transfer process in CdS and Ni(OH)2/Ni3S2/NixS6-CdS. The results confirm that a synergistic effect of Ni(OH)2/Ni3S2/NixS6 on CdS has occurred under light irradiation, where the Ni(OH)2 and nickel sulfides act as hole storage and surface reaction sites, respectively, to promote the charge transfer on CdS. The improved charge transfer and separation efficiency as well as the increased surface reaction sites in Ni(OH)2/Ni3S2/NixS6-CdS finally result in a dramatically improved photocatalytic performance. The photocatalytic H2 evolution rate of Ni(OH)2/Ni3S2/NixS6-CdS is ca. 46 times higher than that of CdS, and the photocatalytic stability of CdS is also improved substantially under visible light irradiation.

Light-Induced Bidirectional Metal-to-Metal Charge Transfer in a Linear Fe2 Co Complex.

It is a challenge to reversibly switch both magnetism and polarity using light irradiation. Herein we report a linear Fe2 Co complex, whereby interconversion between FeIIILS (µ-CN)CoIIHS (µ-NC)FeIIILS (LS=low-spin, HS=high-spin) and FeIIILS (µ-CN)CoIIILS (µ-NC)FeIILS linkages could be achieved upon heating and cooling, or alternating laser irradiation at 808 and 532 nm. The electron spin arrangement and charge distribution were simultaneously tuned accompanying bidirectional metal-to-metal charge transfer, providing switchable polarity and magnetism in the complex.

Magnetic fluorescent bifunctional spin-crossover complexes.

The rational design of magnetic and fluorescent bifunctional materials is attracting increasing interest. In this study, two mononuclear Fe(ii) complexes, namely [Fe(L)2(NCS)2] (1) and [Fe(L)2(NCSe)2] (2) are synthesised by combining a spin-crossover unit and a fluorescent ligand (naphth-1-yl)-N-(3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-yl)methanimine (L) to achieve bifunctionality. Single-crystal X-ray studies and magnetic measurements confirm the presence of spin crossover behaviours; these measurements agree with the results of the temperature depended Raman spectra and infrared spectra. Thermally and light-induced spin crossover is clearly observed for both complexes. The nature of the co-ligand (NCS-vs. NCSe-) shifts the transition temperature by approximately 60 K. The infrared spectra after irradiation reveal that the electronic states are ascribable to the photomagnetic effect at 10 K. Furthermore, temperature-dependent fluorescence emission spectra exhibit the coexistence of spin crossover and fluorescence for 1 and 2.

Single-molecule magnet behavior in three cyano-bridged heterometallic Fe(III)-Ni(II) clusters.

One trinuclear and two tetranuclear cyanide-bridged Fe(III)-Ni(II) complexes were synthesized via treatment of a tricyanometallate with divalent Ni salts in the presence of 1-butylimidazole, 2,2-bipyrimidyl and 1,10-phenanthroline, respectively. Magnetic property studies demonstrated that the three complexes exhibit single-molecule magnet behavior as a result of strong intracluster ferromagnetic coupling and weak intercluster magnetic interactions.

A cyano-bridged tubular coordination polymer with dominant ferromagnetic interactions.

It is a challenge to synthesize a porous tubular coordination polymer with magnetic properties. Utilizing [Fe(II)(bipy)(CN)4](2-) (bipy = 2,2'-bipyridine) as the building block to react with Mn(2+), we successfully synthesized a cyano-bridged tubular coordination polymer with dominant ferromagnetic interactions. The inner surface of the heterometallic tube is hydrophilic, whereas the outer surface is hydrophobic. The framework is stable up to 320 °C and can adsorb N2 and CO2. The ferromagnetic interactions were transmitted via the diamagnetic N-C-Fe(II)-C-N species between Mn(2+) ions in the tube.

Slow magnetic relaxation in a cyano-bridged ferromagnetic {Fe(III)Ni(II)} alternating chain.

A cyano-bridged ferromagnetic {Fe(III)Ni(II)} alternating chain {[Fe(pzTp)(CN)3][Ni(chxn)2]}·ClO4·H2O (1) (pzTp = tetrakis(pyrazolyl)borate, chxn = (1R,2R)-1,2-diaminocyclohexane) was synthesized via rational design. Crystal structure analysis and magnetic studies demonstrated that compound had a one-dimensional zigzagging chain-like structure and slow magnetic relaxation.

New 3d-4f heterometallic clusters built from mixed glycine and iminodiacetate acid: dioctahedron {La2Ni9} and onion-like {Gd5}⊂{Ni12} with interesting magnetocaloric effect.

The preparation, structures and properties of 3d-4f compounds, undecanuclear [La2Ni9(Gly)12(IDA)3(µ3-OH)3][La(H2O)9][Na3(H2O)7(ClO4)3](ClO4)6·5H2O (1) and isostructural heptadecanuclear [Ln5Ni12(Gly)12(IDA)6(µ3-OH)9(H2O)3](ClO4)6·11H2O (Ln = Gd (2); Nd (3); Sm (4); Tb (5); Dy (6); Y (7)) based on mixed glycine (HGly) and iminodiacetate acid (H2IDA) ligands were described. The structure of the [La2Ni9(µ3-OH)3(IDA)3(Gly)12](3+) cationic cluster in 1 can be described as a face-shared and La-centered dioctahedron. However, the [Ln5Ni12(Gly)12(IDA)6(µ3-OH)9(H2O)3](6+) cationic clusters in 2-7 bear an onion-like {Ln5}⊂{Ni12} structure, where the trigonal bipyramid {Ln5} core is encapsulated by the outer triangular orthobicupola {Ni12} shell. Magnetic studies have been performed for these compounds, and 2 displays dominant ferromagnetic coupling and has a large magnetocaloric effect (21.8 J kg(-1) K(-1), ΔH = 7 T).

Two one-dimensional compounds based on pyramidal {TbCu4} units and formate ligand: chair-like [(H2O)2(ClO4)2]2- clusters and slow relaxation of magnetization.

With formate as ligand, two 1-D 3d-4f compounds (linear and zigzag) based on pyramidal {TbCu(4)} unit were obtained. Chair-like [(H(2)O)(2)(ClO(4))(2)](2-) clusters and µ(5)-η(1):η(4) bridging mode of formate were observed in the linear one which also displays slow relaxation of the magnetization.

A spin-crossover cluster of iron(II) exhibiting a mixed-spin structure and synergy between spin transition and magnetic interaction.

How low can you go? An Fe(II) (4) square was prepared by self-assembly and exhibits both thermally induced and photoinduced spin crossover from a system with four high-spin (HS) centers to one with two high-spin and two low-spin (LS) centers. The spin-crossover sites are located on the same side of the square, and the spin transition and magnetic interactions (see picture) are synergistically coupled.

Ligand-to-metal ratio controlled assembly of nanoporous metal-organic frameworks.

Two bilayered metal-organic frameworks with nanoporous channels were synthesized at different ligand-to-metal ratios, which demonstrated an interesting crystal-to-crystal transformation property and a special fluorescent response to the different guest molecules included.

Thiourea-based molecular clips for fluorescent discrimination of isomeric dicarboxylates.

A new clip-like receptor, which comprises two thiourea-based binding groups and two naphthalene units, has been designed and synthesized as a fluorescent chemosensor for distinguishing o-phthalate from two other isomers of dicarboxylates. Upon the addition of these three ions, the emission intensity at 420 nm (excitation at 340 nm) decreases drastically through PET. When excited at 380 nm, a new emission band at 460 nm appears and develops gradually upon the addition of the o-phthalate ion and the fluorescent intensity increases markedly over time, but the presence of m-phthalate or p-phthalate do not cause this kind of change. It suggests a guest-induced "off-on" conformational switching signaling transduction. The presence of the o-phthalate anion induces a special conformation with two naphthalene units positioned close enough to exhibit a new emission.

Metal complexes formed by metal-assisted solvolysis of di-pyridylketone azine: structures and magnetic properties.

A series of metal complexes were achieved from the metal-assisted solvolysis reaction of di-pyridylketone azine (dpka). The tetranuclear nickel cluster , [Ni(2)[dpk(O)(OH)][dpk(O)(OCH(3))](N(3))(2)](2), is centrosymmetric with a central core described as an edge-shared triangle core. Neighboring Ni(II) ions are alternately bridged by (micro(2)-N(3), micro(3)-O) and (micro(2)-O, micro(3)-O) double bridges. Complex , [Cu(4)[dpk(O)(OCH(3))](4)(N(3))(2)](CuCl(2))(2) contains a tetranuclear cluster and two identical [CuCl(2)]M(-) anions. The tetranuclear structure has two crystallographically imposed twofold axes, in which the four copper ions are arranged to be rhombic shape. The neighboring copper(ii) ions along the lateral are bridged by single micro(2)-O from the ligand dpk(O)(OCH(3)) and the short diagonal copper ions are bridged by two symmetric end-on azides. In dinuclear Cu(ii) complex [Cu(2)[dpka(OCH(2)CH(3))]Cl(2)](ClO(4)) (3), the metal centers are coordinated in a planar configuration and bridged by a -N-N- bridge. It is also observed that the Cl atom coordinated to one Cu(II) center is also weakly coordinated to another inversion related Cu(II) to generate a centrosymmetric dimer. The metal centers in one-dimensional polymeric Cu(ii) complex [Cu(2)[dpka(OCH(3))](N(3))(2)(ClO(4))](n) (4), however, are bridged by a -N-N- bridge and an end-to-end azide bridge, alternately. Magnetic susceptibility measurements indicate that shows ferromagnetic interaction within the tetranuclear cluster, and that displays moderately strong antiferromagnetic interaction (J = -56.7 cm(-1)) for the bis(micro-N(3)) bridge. For compound , it shows strong antiferromagnetic coupling (J = -286 cm(-1)) between the intradinuclear Cu(II) ions mediated by the single N-N bridge and negligible magnetic interactions between the adjacent dinuclear Cu(II) ions mediated by the single end-to-end azide bridge. The mechanism of the metal-assisted solvolysis reaction was also discussed.