Porphyrin-Sensitizers and Anthracene-Annihilators Built in Isostructural Frameworks for Investigating Triplet-Triplet Annihilation Upconversion.

In this study, four isostructural pillar-layered frameworks were constructed using a porphyrin layer and an anthracene pillar, which served as the sensitizer and annihilator, respectively, in the triplet-triplet annihilation upconversion (TTA-UC) system. Framework 1 demonstrated the highest upconversion quantum yield of 1.01%. Additionally, 1 and 2 also exhibited down-conversion fluorescence resulting from the porphyrin component. A twist intramolecular charge transfer (TICT) state was observed in the bianthracene chromophore of 2, resulting in transient rotation of two anthracene rings and red-shifted emission. Both computational studies and experiments confirmed the transition from a locally excited state to a TICT state upon the inclusion of polar guest molecules into the framework.

Polypyridyl Ru(II) or cyclometalated Ir(III) functionalized architectures for photocatalysis.

The chemistry of polypyridyl Ru(II) and cyclometalated Ir(III) derivatives provides long-lasting interest to researchers due to the inherent advantage of their triplet states in a variety of photoactivities. The introduction of Ru(N^N)3 and Ir(C^N)2(X^N) modules into well-defined architectures extends the research areas of both photoactive metal complexes and network chemistry, generating a lot of new opportunities with interesting structural aesthetics and profound functional possibilities. The rapid development of research in integrating Ru(II) or Ir(III) metallotecons into the architectures has been apparent in recent years which makes this a fascinating subject for reviewing. This review focuses on the design and syntheses of Ru(N^N)3 and Ir(C^N)2(X^N) functionalized architectures of metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), metallasupramolecules, organic supramolecules and supramolecular organic frameworks (SOFs). Furthermore, the photocatalytic applications including the hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), photocatalytic oxidation and photoredox catalysis of organic transformation are also presented.

Enhancement in Two-Photon Absorption and Photoluminescence in Single Crystals of Cd(II) Metal Organic Frameworks.

The emergence of metal organic frameworks (MOFs) as advanced photonic materials has placed them at the forefront of exploration. Nonlinear optical (NLO) phenomena such as simultaneous two-photon absorption and consequent upconversion emission have been in demand for promising applications. A rational design approach based on the fundamental structure-property relationship is key for the fabrication of nonlinear optically active MOF materials. Here, we investigate two-photon-absorption (2PA)-induced photoluminescence of four new Cd(II) MOFs based on an acceptor-π-donor-π-acceptor trans, trans-9, 10-bis(4-pyridylethenyl)anthracene chromophore linker. The use of auxiliary carboxylate linkers resulted in the variation of crystal structures, leading to the modulation of NLO properties. On comparison with a standard Zn(II)-MOF, two MOFs showed enhancement in 2PA, while the other two showed a mild decrease. We tried to establish a structural correlation to explain the trend in NLO activity. The interplay of various factors such as chromophore density, degree of interpenetration, chromophore orientation, and π···π interactions between the individual networks affects the NLO activities. These results show the modulation of the optical properties of MOFs based on a combined strategy for the development of tunable single crystal NLO devices.

Photoreactive Crystals Exhibiting [2 + 2] Photocycloaddition Reaction and Dynamic Effects.

ConspectusConducting a reaction in the solid state eliminates the usage of solvents. If such reactions are conducted in a single-crystal to single-crystal (SCSC) fashion, then structural characterization by single-crystal X-ray crystallography (SCXRD) techniques provides unequivocal structural details. Although topochemical principles govern, getting single crystals at the end of a SCSC reaction purely depends on the experimental skills of the researchers. SCSC reactions are common among solid-state [2 + 2] cycloaddition reactions (hereafter "photoreaction") after the classical work of Schmidt and co-workers in 1960s. Synthons and tectons in the crystal engineering box can be exploited to bring the functional groups into the required alignment and packing to achieve the desired chemical reactivities and physical properties, respectively. Bringing a pair of alkenes closer together in the organic molecules provides an effective starting point to achieve the goal of crystal engineering.Further, understanding and controlling photoreactivity in the solid state provide a gateway to designing new advanced materials, for example, making cycloreversible optical storage materials, photosalient and photomechanical materials, highly crystalline or even single-crystalline organic polymers, covalent organic framework structures, and organic polymers incorporated inside metal-organic frameworks (MOFs). Photoreactions often proceed in a SCSC manner due to the limited movements of the closely disposed reactive functional groups in the crystals. Thus, these photoreactions yield not only quantitative photoproducts but also regio- and stereospecificity, which are otherwise inaccessible by solution syntheses.The traditional definition of crystals being hard, rigid, and brittle is no longer valid ever since the mechanically responsive crystals were discovered. These dynamic crystals undergo various movements like curling, jumping, hopping, popping, splitting, and wiggling, when exposed to light (called "photosalient effect") or heat (called "thermosalient" effect). These crystals generate new methods of transforming light and heat energy into mechanical work. Recently, photosalient behavior during the [2 + 2] cycloaddition reaction under UV light has been frequently observed. With the emergence of the field of "crystal adaptronics", dynamic photoreactive crystals have emerged as smart actuating materials.This Account aims to provide an overview of the development in this area, since it has garnered much attention among solid state chemists. While presenting selected examples of important strategies, we try to illustrate the intentions and concepts behind the methods developed, which will help in a rational approach for the fabrication of advanced solid state materials. Apart from topochemical transformations, the important roles played by weak interactions, guest solvents, and mechanical grinding have been highlighted in several classes of compounds to show structural transformations that defy the expected outcomes. Overall, the progress of [2 + 2] cycloaddition reaction in solid state materials has been discussed from UV induced structural transformations to the development of smart actuating materials.

Highly Efficient Multiphoton Absorption of Zinc-AIEgen Metal-Organic Frameworks.

A series of luminescent frameworks was synthesized from the selective combination of aggregation induced emission (AIE)-linker tetra-(4-carboxylphenyl)ethylene (H4 TCPE) and Zn2+ . Complex 1 was formed by the close packing of Zn-TCPE hinge, and isostructural complexes 2-5 were constructed by the linkage of Zn-TCPE layer and pillar ligands. These complexes exhibit highly efficient multiphoton excited photoluminescence (MEPL) and concomitant third-harmonic generation (THG). The multiphoton absorption (MPA) parameters of 1 are superior to other multiphoton emission materials including the perovskite nanocrystals. The incorporation of pillar linkers slows down the charge transfer between layers of Zn-TCPE, and the aromatic core of pillar linkers has a great influence on the MPA performance of the corresponding frameworks.

Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties.

A change in the degree of interpenetration (DOI) in metal-organic frameworks (MOFs) prompted by heat, pressure, or exchange of solvents is a fascinating phenomenon that can potentially impact the functional properties of MOFs. Structural transformation involving two noncentrosymmetric MOFs with different DOIs provides a rare opportunity to manipulate their optical properties. Herein, we report an unusual single-crystal-to-single-crystal (SCSC) transformation of a noncentrosymmetric 7-fold interpenetrated diamondoid (dia) Cd(II) MOF into another noncentrosymmetric but 8-fold interpenetrated dia MOF upon the removal of guest solvents. A hydrogen-bond network formed between the lattice solvents and linker trans-2-(4-pyridyl)-4-vinylbenzoate (pvb) in a 7-fold interpenetrated noncentrosymmetric MOF results in a significant increase in the two-photon absorption cross-section (11 times) as compared to that in the desolvated 8-fold interpenetrated MOF. Also, an increase in the DOI in the noncentrosymmetric crystals strengthened the π···π interaction between the individual diamondoid networks and enhanced the second-order nonlinear optical (NLO) coefficient (deff) by 4.5 times. These results provide a way to manipulate the optical properties of MOFs using a combined strategy of the formation of hydrogen bonds and interpenetration for access to tunable single-crystal NLO devices in an SCSC manner. By changing the experimental conditions, another dia Cd(II) MOF with 4-fold interpenetration can be isolated. In this centrosymmetric MOF, the olefin groups in the backbone of the ligand (pvb) undergo a [2 + 2] cycloaddition reaction quantitatively under UV light but in a non-SCSC fashion.

Anisotropic Two-Photon Absorption and Second Harmonic Generation in Single Crystals of Silver(I) Coordination Complexes.

Metal complexes have been gaining attention in recent times over the traditional inorganic materials such as nonlinear optical materials. Here, we report both two-photon absorption (2PA) and second harmonic generation (SHG) from single crystals of two Ag(I) complexes with considerable optical anisotropy. We demonstrate that by controlling the incident light polarization, the tunability between these two nonlinear optical processes can be achieved. The deff values of the observed SHG from one complex are determined to be one order of magnitude greater than ß-BBO crystals.

Construction of 2D Interdigitated Polyrotaxane Layers and their Transformation to a 3D Polyrotaxane by a Photocycloaddition Reaction between Wheels.

Following the pioneering work of Sauvage and Stoddart on rotaxanes, construction of higher dimensional polyrotaxanes in metal-organic frameworks (MOFs) via a modified protocol is challenging. We present the formation of a two-dimensional (2D) polyrotaxane and its conversion to a three-dimensional (3D) polyrotaxane MOF via a photoreaction between interdigitated "olefin wheels". For this purpose, a 2-fold entangled 2D MOF [Pb2(bpp)(sdc)2] (1), showing a 2D + 2D → 2D polyrotaxane motif, has been synthesized from the solvothermal reaction of lead(II) nitrate, 3,3'-stilbenedicarboxylic acid (H2sdc) containing an olefin group, and 1,4-bis(4-pyridyl)piperazine (bpp). The single-crystal X-ray diffraction analysis of 1 revealed that the adjacent entangled 2D layers are interdigitated, with the separation of 3.72 Šbetween C═C bond pairs in adjacent layers satisfying Schmidt's criteria for the occurrence of a [2 + 2] photocycloaddition reaction. Irradiation of the single crystals of 1 under UV light resulted in formation of a 3D polyrotaxane, [Pb2(bpp)(rctt-tccb)]n (2), due to a [2 + 2] photocycloaddition reaction between two wheels via a single-crystal to single-crystal transformation. The photocycloaddition and partial thermal cleavage reaction between 1 and 2 were confirmed by 1H NMR and powder X-ray diffraction (PXRD) in solution and the solid state, respectively. The present approach could contribute to the understanding of the construction of higher dimensional polyrotaxanes which are not accessible by the traditional routes.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications.

Among the recent developments in metal-organic frameworks (MOFs), porous layered coordination polymers (CPs) have garnered attention due to their modular nature and tunable structures. These factors enable a number of properties and applications, including gas and guest sorption, storage and separation of gases and small molecules, catalysis, luminescence, sensing, magnetism, and energy storage and conversion. Among MOFs, two-dimensional (2D) compounds are also known as 2D CPs or 2D MOFs. Since the discovery of graphene in 2004, 2D materials have also been widely studied. Several 2D MOFs are suitable for exfoliation as ultrathin nanosheets similar to graphene and other 2D materials, making these layered structures useful and unique for various technological applications. Furthermore, these layered structures have fascinating topological networks and entanglements. This review provides an overview of different aspects of 2D MOF layered architectures such as topology, interpenetration, structural transformations, properties, and applications.

Reversible Thermosalience in a One-Dimensional Coordination Polymer Preceded by Anisotropic Thermal Expansion and the Shape Memory Effect.

Thermally responsive crystals hold great potential for their use as actuating materials by acting as energy transducers to convert heat energy to mechanical work. Control over defined phase transition temperature with rapid reconfiguration is of great advantage for actuation. The thermosalient (TS) effect is a rarely observed phenomenon in coordination polymers (CPs), let alone the reversibility of thermosalience in CPs. Herein, we report the reversible TS effect in a one-dimensional CP due to the martensitic phase transition during both heating and cooling cycles. The TS effect was preceded by anisotropic thermal expansion showing high expansion coefficients. In addition, the nonmolecular crystals show reversible contraction and recovery during multiple heating-cooling cycles due to the self-restorative shape memory effect. The reversible actuation of the CP could be repeated for 20 heating-cooling cycles in differential scanning calorimetry experiments, suggesting its great potential as a multicyclic actuator. Such thermal responsive behavior is unique in metal-organic materials.

Single-Crystal-to-Single-Crystal [2 + 2] Photocycloaddition Reaction in a Photosalient One-Dimensional Coordination Polymer of Pb(II).

In a remarkable example, we report a one-dimensional coordination polymer (CP) of Pb(II) showing photosalient (PS) properties triggered by [2 + 2] cycloaddition of olefinic ligands, which is seldom observed in CPs. Macroscopic rod-shaped crystals show various photomechanical effects such as jumping, splitting, rolling, and breaking upon UV illumination. In this rare example, we could determine the solid-state structure of the 100% dimerized product and three intermediate structures, even after the shattering of crystals into small pieces. Detailed mechanistic investigation from the single-crystal data indicates that the strain generated in the unit cell due to anisotropic expansion played a bigger role for the PS effects. Nucleated growth of the photoproduct crystal created different domains inside the single crystal, which multiplied the already developed stress leading to the photomechanical movements. This example falls in the gray area of a clean single-crystal-to-single-crystal (SCSC) transformation and violent PS effect. Such photochemical behavior has never been reported before.

Water Stable Zn(II) Metal-Organic Framework as a Selective and Sensitive Luminescent Probe for Fe(III) and Chromate Ions.

Sensing and monitoring toxic contaminants like Fe3+, CrO42-, and Cr2O72- ions in water is very important due to their harmful effects on biological and environmental systems. Enhanced hydrolytic stability, sensitivity, and selectivity, in addition to their excellent luminescence properties, are important attributes of metal-organic framework (MOF)-based sensors for sensing applications. In this work, the water stable Zn-MOF [Zn2(tpeb)(bpdc)2] (where tpeb = 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene and bpdc = biphenyl-4,4'-dicarboxylic acid) was synthesized and characterized. The framework retains its crystallinity and structural integrity in harsh acidic and basic conditions (pH 4-11). Most interestingly, the Zn-MOF demonstrates a strong blue luminescence in water that can be quenched selectively only by contaminants like Fe3+, CrO42-, and Cr2O72- ions. Higher Ksv values and low detection limits in selective luminescence quenching confirm the superior sensing performance, which is comparable to those of contemporary materials. Furthermore, in all cases, quenching efficiency remains unaltered in the presence of interfering ions, even after the compound is used in multiple cycles, which makes this MOF an attractive, reliable, and recyclable luminescent sensor material. The luminescence quenching mechanism is based on the competitive absorption and weak interactions. It is worth noting that most of the reported MOF-based sensors used for the separate sensing of Fe(III) and chromate ions are used in organic media due to their poor hydrolytic stabilities. Reports on the dual sensing of Fe(III) and chromate ions, which are also in aqueous media, are rare. Based on these results, Zn-MOF can be considered as a suitable candidate for advanced practical applications for the efficient sensing of Fe(III) and chromate ions in water.

Rotation of a helical coordination polymer by mechanical grinding.

Anisotropic cell volume expansion by mechanical grinding of the solid facilitates the concerted rotation of the photo-inert helical coordination polymer, which causes the misaligned arms containing olefin functional groups in the neighbouring strands to align to undergo [2+2] cycloaddition reaction in 83% yield.

Disappeared supramolecular isomer reappears with perylene guest.

Among different types of polymorphism, disappearing polymorphism deals with the metastable kinetic form which can not be reproduced after its first isolation. In the world of coordination polymers (CPs) and metal-organic frameworks (MOFs), despite the fact that many types of supramolecular isomerism exist, we are unaware of disappearing supramolecular isomerism akin to disappearing polymorphism. This work reports a MOF with dia topology that could not be reproduced, but subsequent synthesis yielded another supramolecular isomer, a double-pillared-layer MOF. When perylene was added in the same reaction, the disappeared dia MOF reappeared with perylene as a guest in the channels. Interestingly, the photoluminescence of the dia MOF with a perylene guest is dominated by the emission of the guest molecule. The influence of guest molecules on the stabilization of the supramolecular isomers of a MOF opens up a strategy to access MOFs with different structures.

Extraordinary anisotropic thermal expansion in photosalient crystals.

Although a plethora of metal complexes have been characterized, those having multifunctional properties are very rare. This article reports three isotypical complexes, namely [Cu(benzoate)L 2], where L = 4-styryl-pyridine (4spy) (1), 2'-fluoro-4-styryl-pyridine (2F-4spy) (2) and 3'-fluoro-4-styryl-pyridine (3F-4spy) (3), which show photosalient behavior (photoinduced crystal mobility) while they undergo [2+2] cyclo-addition. These crystals also exhibit anisotropic thermal expansion when heated from room temperature to 200°C. The overall thermal expansion of the crystals is impressive, with the largest volumetric thermal expansion coefficients for 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10-6 K-1, respectively, values that are comparable to only a handful of other reported materials known to undergo colossal thermal expansion. As a result of the expansion, their single crystals occasionally move by rolling. Altogether, these materials exhibit unusual and hitherto untapped solid-state properties.

Giant Enhancement of Second Harmonic Generation Accompanied by the Structural Transformation of 7-Fold to 8-Fold Interpenetrated Metal-Organic Frameworks (MOFs).

Interpenetration in metal-organic frameworks (MOFs) is an intriguing phenomenon with significant impacts on their properties, and functional applications. Herein, we show that a 7-fold interpenetrated MOF (1) is transformed into an 8-fold interpenetrated MOF by the loss of DMF in a single-crystal-to-single-crystal manner. This is accompanied by a giant enhancement of the second harmonic generation (SHG ca. 125 times) and two-photon photoluminescence (ca. 14 times). The strengthened π-π interaction between the individual diamondoid networks and intensified oscillator strength of the molecules aid the augment of dipole moments and boost the nonlinear optical conversion efficiency. Large positive and negative thermal expansions of 1 occur at 30-150 °C before the loss of DMF. These results offer an avenue to manipulate the NLO properties of MOFs using interpenetration and provide access to tunable single-crystal NLO devices.

Straight, bendable and bent organic crystals.

trans-4-Phenylazobenzoic acid (pab) crystallized in three different morphologies: long rod-like crystals, bendable long thin crystals, and bent crystals. Of them, the bent crystals were obtained by recrystallizing after subjecting pab to UV-irradiation in solution. A small amount of cis-form in the bent crystals is responsible for the bent nature, while the elastic bending of thin platy crystals can be understood from the crystal packing.

Chemical Patterning in Single Crystals of Metal-Organic Frameworks by [2+2] Cycloaddition Reaction.

Conventional chemical patterning involves films of polymeric materials. Herein, we demonstrate that the presence or absence of guest solvents in the crystal voids modulates the patterning of the cyclobutane rings in highly strained metal-organic frameworks (MOFs) under UV light. The olefin pairs of the spacer ligands, which resemble a ladder-like structure, in the MOF, undergo a [2+2] cycloaddition reaction in a single-crystal-to-single-crystal manner. For instance, a partial photoreaction in the MOFs in the absence of a guest solvent as well as with dimethylacetamide in the voids generated two different patterns of the cyclobutane rings. Surprisingly, the MOF with the lattice dimethylformamide undergoes 100 % photoreaction, but the photoproduct contains broken chains. Such chemical patterning at the molecular level represents a next step in crystal engineering.

Solid-State Photochemical [2+2] Cycloaddition Reaction of MnII Complexes.

Three MnII complexes have been synthesized under similar experimental conditions. Of these [Mn2 (benzoate)4 (L)2 ] (where L=4-styrylpyridine or 4spy, 1 and 2-fluoro-4'-styrylpyridine or 2F-4spy, 3) are paddlewheel complexes, but crystallized in different space groups. Whereas [Mn2 (benzoate)4 (3F-4spy)4 ] (3F-4spy=3-fluoro-4'-styrylpyridine), 4 is a dinuclear complex having different stoichiometry from 1 and 3 with two pairs of 3F-4spy ligands aligned in face-to-face manner. An irreversible phase transition occurs from the space group P21 /c to C2/c when 1 was heated up to 125 °C to 2 in a single-crystal-to-single-crystal fashion or when ground 1 to powder. 2 is isomorphous and isostructural to 3. Complimentary π-π interactions in head-to-tail alignment of the styrylpyridine ligands furnishes 1D aggregates in 1-3 which are congenial to undergo [2+2] cycloaddition reaction under UV light. Whereas, face-to-face alignment of the 4spy pairs in 4 is expected to provide a head-to-head photoproduct. All the MnII complexes are indeed found to be photoreactive. To our surprise, contrary to their ZnII analogues, 2 and 3 were not found to be photosalient. The percentage volume expansion during the photoreaction as determined from the density measurements, was found to be too low (3.2 and 4.6 % respectively for 2 and 3) to have this behavior.

Near-White Light Emission from Lead(II) Metal-Organic Frameworks.

Reaction of bpy (bpy = 4,4'-bipyridine) with Pb(OAc)2·3H2O in DMF (DMF = dimethylformamide) afforded a metal-organic framework (MOF), [Pb2(µ-bpy)(µ-O2CCH3)2(µ-O2CCH3)2]·H2O (1). Reaction of bpy with Pb(O2CCF3)2 in a methanol and chloroform mixture furnished another MOF, [Pb(µ-bpy)(µ-O2CCF3)2]·1/2CHCl3 (2). However, the reaction of bpy with Pb(OAc)2·3H2O in the presence of trifluoroacetic acid in a similar reaction condition yielded a hydrogen-bonded zwitter-ionic complex of Pb(II), [Pb(bpy-H)2(O2CCF3)4] (3). All compounds have been characterized by single crystal X-ray crystallography, FT-IR, and 1H NMR spectroscopies. Compound 1 forms four heptacoordinated Pb(II) joined by (OCCH3)-O- linkages, resulting in a 3D noninterpenetrated MOF net with a four-connected uninodal sra (SrAl2) topology. However, in 2, tetra-connected Pb4(O2CCF3)8 cluster units are linked further through eight bpy ligands to furnish a doubly interpenetrated MOF with a new topology but having the very similar connectivity of 1, whereas 3 forms a zigzag hydrogen-bonded chain structure. The variation of carboxylate anions, pH of the reaction medium, and the ratio of the reactants profoundly affected the final topological structure of the compounds synthesized. The solid-state photoluminescence of 1-3 was investigated at room temperature. Interestingly 1, 2, and 3 achieved close to white light emission when excited at 329, 376, and 330 nm, respectively. The systematic understanding of the photophysical properties of analogous Pb-based compounds may open new perspectives for developing single-phase white-light-emitting materials using Pb(II) based MOFs.