Light driven mesoscale assembly of a coordination polymeric gelator into flowers and stars with distinct properties

Mukhopadhyay, Rahul; Praveen, Vakayil K.; Hazra, Arpan; Maji, Tapas Kumar; Ajayaghosh, Ayyappanpillai

doi:10.1039/c5sc02233a

Cited by 65 publications

(48 citation statements)

References 77 publications

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“…Morris and co‐workers used the degradation of a UiO‐type MOF with AB photoswitches in the backbone to achieve a UV‐light‐induced release of Nile red molecules . Using such linker molecules, the MOF morphology can also be modulated by trans–cis switching of the linker molecules before MOF synthesis …”

Section: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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In recent years, a particularly attractive and novel strategy has become available for the fabrication of photoresponsive, porous, and crystalline molecular solids from appropriately functionalized chromophoric linkers. The crystallinity of these materials allows a rather straightforward description and analysis using theoretical methods, thus tremendously accelerating the design of novel materials. This new class of crystalline molecular solids is referred to as metal-organic frameworks, MOFs (or porous coordination polymers, PCPs). [1] MOFs are constructed from metal-/metal-oxo nodes and organic linkers (Figure 1). The incorporation of photoactive species into MOFs may be realized by using them as linkers (method L) or attaching them to a linker (method A), as shown in Figure 1a. In addition, the porosity of MOFs allows the loading of chromophoric compounds as guests (method G) into the pores of this interesting framework material.In this review article, we mainly focus on organic photoactive species, which are either simply loaded as guests into porous MOFs or used after appropriate functionalization as building blocks for the construction of the framework (methods L, A, and G). [2] It is important to note that in the context of photoresponsive behavior, MOFs carry a potential which by far exceeds that of nonporous coordination polymers. This is because simple loading of guest/solvent molecules of different size/polarity/functionality in the MOF pores can impart a large optical response, which is useful, e.g., for sensing applications. [3] As an example, the solvent-dependent optical response or solvatochromism [4] is illustrated in Figure 1b. Such effects cannot be realized for nonporous coordination polymers.The different types of photoresponsive molecules addressed in this review can be grouped into two classes. The first contains molecules where the structure remains essentially unchanged upon light-induced electronic excitation, and the second contains molecular species that change their structure or conformation upon absorption of photons (molecular switches).Light with a wavelength in the range 200-800 nm (6.2-1.5 eV) can excite a molecule to a transient excited electronic state. The transient state then decays to a low-energy state, either the parent ground state or another longer-lived excited state. Decay time scales are in the range 10 −12 -10 1 s, and the released energy can be radiative or nonradiative in nature. For many applications, nonradiative energy loss is unwanted, When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well-defined structure carry substantial advantages over amorphous materials. Here, the metal-organic framework (MOF)-based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coo...

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Section: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…Metallogels [5,[26][27][28][29][30][31] are as pecialt ype of supramolecular gel, wherein metal-ligand coordination along with other noncovalent interactions play important roles in forming SAFiNs. Coordination polymers, [32,33] crossed-linked coordination polymers, [34] and coordination complexes [27,35] have been reported to form metallogels.…”

Section: Introductionmentioning

confidence: 99%

Rational Approach Towards Designing Metallogels From a Urea‐Functionalized Pyridyl Dicarboxylate: Anti‐inflammatory, Anticancer, and Drug Delivery

Dastidar

2018

Chemistry An Asian Journal

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As tructural rationalew as adopted to design a series of metallogels from an ewly synthesized urea-functionalized dicarboxylate ligand, namely,5 -[3-(pyridin-3-yl)ureido]isophthalic acid( PUIA), that produces metallogels upon reaction with various metal salts (Cu II ,Z n II ,C o II ,C d II ,a nd Ni II salts) at room temperature. Theg els werec haracterized by dynamic rheology and transmission electron microscopy (TEM). The existence of ac oordination bond in the gels tate was probed by FTIR and 1 HNMR spectroscopy in aZ n II metallogel (i.e., MG2). Single crystals isolated from the reaction mixture of PUIA and Co II or Cd II salts characterized by X-ray diffraction revealed lattice inclusiono fs olvent molecules, which was in agreement with the hypothesis based on which the metallogels were designed. MG2 displayed antiinflammatory response (prostaglandin E 2 assay) in the macrophage cell line (RAW264.7) and anticancer properties (cell migration assay) on ah ighly aggressive human breast cancer cell line (MDA-MB-231). The MG2 metallogel matrix could also be used to load and release( pH responsive) the anticancer drug doxorubicin. Fluorescence imaging of MDA-MB-231 cellst reated with MG2 revealed that it was successfully internalized.

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“…It is commonly believed that, under suitable conditions, gelator molecules self‐assemble into self‐assembled fibrillar networks (SAFiNs), within which solvent molecules are immobilized . Such gels that contain metal ions as an integral part are called “metallogels” . Various gelating agents have been reported to effect metallogel formation, including discrete metal‐coordination complexes, well‐defined coordination polymers, and cross‐linked coordination polymers .…”

Section: Introductionmentioning

confidence: 99%

“…[13][14][15][16] Such gels that contain metal ions as an integral part are called "metallogels". [17][18][19][20] Various gelating agents have been reported to effect metallogel formation,i ncluding discrete metal-coordination complexes, [21] well-defined coordination polymers, [22][23][24] and cross-linked coordination poly-mers. [25] In each case, highly directional metalÀligand bonds govern the self-assembly process to generate af ibrous network of metallogels.I nr ecent years, metallogels have flourished as ap romisingf ield of research, owing to their applications in sensors, [26] proton conduction, [27,28] magnetic materials, [29] catalysis, [30] and nanoparticle templating.…”

Section: Introductionmentioning

confidence: 99%

Rheoreversible Metallogels Derived from Coordination Polymers

Ganguly

Parveen

Dastidar

2018

Chemistry An Asian Journal

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A series of mixed-ligand-based Cd /Co coordination polymers (CPs) that were derived from two bis(pyridyl)-bis(amide) ligands, 4,4'-oxybis(N-(pyridin-3-yl)benzamide) (LP) and 4,4'-oxybis(N-(pyridin-4-yl)benzamide) (LP1), and a variety of dicarboxylates isophthalates, terephthalates, 1,2-carboxytranscinamates, and 1,3- and 1,4-phenylene dicarboxylates were synthesized based on a rationale that they would occlude solvate guests inside their crystal lattice, thereby rendering these CPs suitable as metallogelators. The CPs were characterized by using single-crystal X-ray diffraction, elemental analysis, powder X-ray diffraction (PXRD), FTIR spectroscopy, and thermogravimetric analysis (TGA). Structural analyses revealed that the majority of the CPs were lattice-occluded molecular solids, which provided us with an opportunity to study their gelation behavior. We observed that, out of eight CPs that were tested, seven were able to produce metallogels. A thorough study of the rheological behavior of the metallogels was performed and CPG1, CPG2, CPG4, and CPG5 were found to exhibit rheoreversible behavior, which was further confirmed by rheological experiments. Interestingly, ligand LP was found to form an aqueous gel, which was exploited to produce silver nanoparticles.

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Light driven mesoscale assembly of a coordination polymeric gelator into flowers and stars with distinct properties

Abstract: Photoinduced coordination modulation varies the morphology of the coordination polymeric gel from flowers to stars, with different viscoelastic and gas adsorption properties.

Cited by 65 publications

References 77 publications

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Rational Approach Towards Designing Metallogels From a Urea‐Functionalized Pyridyl Dicarboxylate: Anti‐inflammatory, Anticancer, and Drug Delivery

Rheoreversible Metallogels Derived from Coordination Polymers

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