We report the design and synthesis of an amide functionalized microporous organic polymer (Am-MOP) prepared from trimesic acid and p-phenylenediamine using thionyl chloride as a reagent. Polar amide (-CONH-) functional groups act as a linking unit between the node and spacer and constitute the pore wall of the continuous polymeric network. The strong covalent bonds between the building blocks (trimesic acid and p-phenylenediamine) through amide bond linkages provide high thermal and chemical stability to Am-MOP. The presence of a highly polar pore surface allows selective CO2 uptake at 195 K over other gases such as N2, Ar, and O2. The CO2 molecule interacts with amide functional groups via Lewis acid-base type interactions as demonstrated through DFT calculations. Furthermore, for the first time Am-MOP with basic functional groups has been exploited for the Knoevenagel condensation reaction between aldehydes and active methylene compounds. Availability of a large number of catalytic sites per volume and confined microporosity gives enhanced catalytic efficiency and high selectivity for small substrate molecules.

We report the design and synthesis of two porous graphene frameworks (PGFs) prepared via covalent functionalization of reduced graphene oxide (RGO) with iodobenzene followed by a C-C coupling reaction. In contrast to RGO, these 3D frameworks show high surface area (BET, 825 m(2) g(-1)) and pore volumes due to the effect of pillaring. Interestingly, both the frameworks show high CO2 uptake (112 wt% for PGF-1 and 60 wt% for PGF-2 at 195 K up to 1 atm). PGFs show nearly 1.2 wt% H2 storage capacity at 77 K and 1 atm, increasing to ∼1.9 wt% at high pressure. These all carbon-based porous solids based on pillared graphene frameworks suggest the possibility of designing related several such novel materials with attractive properties.

A superhydrophobic self-cleaning MOF nanostructure has been synthesized using a unique ligand design strategy and coordination directed self-assembly. The material has hierarchical surface roughness and is stable under extreme corrosive conditions.

We report the synthesis, structural characterization, and porous properties of two isomeric supramolecular complexes of ([Cd(NH2 bdc)(bphz)0.5 ]⋅DMF⋅H2 O}n (NH2 bdc=2-aminobenzenedicarboxylic acid, bphz=1,2-bis(4-pyridylmethylene)hydrazine) composed of a mixed-ligand system. The first isomer, with a paddle-wheel-type Cd2 (COO)4 secondary building unit (SBU), is flexible in nature, whereas the other isomer has a rigid framework based on a μ-oxo-bridged Cd2 (μ-OCO)2 SBU. Both frameworks are two-fold interpenetrated and the pore surface is decorated with pendant -NH2 and NN functional groups. Both the frameworks are nonporous to N2 , revealed by the type II adsorption profiles. However, at 195 K, the first isomer shows an unusual double-step hysteretic CO2 adsorption profile, whereas the second isomer shows a typical type I CO2 profile. Moreover, at 195 K, both frameworks show excellent selectivity for CO2 among other gases (N2 , O2 , H2 , and Ar), which has been correlated to the specific interaction of CO2 with the -NH2 and NN functionalized pore surface. DFT calculations for the oxo-bridged isomer unveiled that the -NH2 group is the primary binding site for CO2 . The high heat of CO2 adsorption (ΔHads =37.7 kJ mol(-1) ) in the oxo-bridged isomer is realized by NH2 ⋅⋅⋅CO2 /aromatic π⋅⋅⋅CO2 and cooperative CO2 ⋅⋅⋅CO2 interactions. Further, postsynthetic modification of the -NH2 group into -NHCOCH3 in the second isomer leads to a reduced CO2 uptake with lower binding energy, which establishes the critical role of the -NH2 group for CO2 capture. The presence of basic -NH2 sites in the oxo-bridged isomer was further exploited for efficient catalytic activity in a Knoevenagel condensation reaction.

Rationalization of structure and properties of amorphous porous solids at the microscopic level is essential in developing advanced materials. We delineate the structural modeling of a designed tetraphenylethene-based amorphous conjugated microporous polymer TPE-CMP (1) and its gas storage and photophysical properties. The polymer 1 exhibits high specific surface area of 854 m 2 /g. 1 showed appreciable CO 2 (32.4 wt %) uptake at 195 K up to 1 atm and 31.6 wt % at 273 K up to 35 bar. The structural model of 1 obtained through computational methods is quantitatively consistent with experimental observations. The microporous structural model of 1 was further validated by a calculation of CO 2 adsorption isotherm obtained through GCMC simulations. Quantum chemical calculations were employed to understand the nature of interactions of CO 2 with the constituents of the framework 1. π−π interaction with strength of 19 kJ/mol was observed between CO 2 and the phenyl rings of TPE. 1 shows strong turn-on greenish-yellow emission due to the restriction of phenyl ring rotation of TPE node. This framework induced emission (FIE) of microporous polymer 1 is further exploited for light-harvesting applications by noncovalent encapsulation of a suitable acceptor dye, rhodamine B (RhB), in the framework.

A new blue emissive gelator has been synthesized and its self-assembly with TbIII and EuIII results in coordination polymer gels, which show tunable emission based on stoichiometric control over LMWG:TbIII:EuIII.

The process of assembling astutely designed, well-defined metal-organic cube (MOC) into hydrogel by using a suitable molecular binder is a promising method for preparing processable functional soft materials. Here, we demonstrate charge-assisted H-bonding driven hydrogel formation from Ga3+-based anionic MOC ((Ga8(ImDC)12)12−) and molecular binders, like, ammonium ion (NH4+), N-(2-aminoethyl)-1,3-propanediamine, guanidine hydrochloride and β-alanine. The morphology of the resulting hydrogel depends upon the size, shape and geometry of the molecular binder. Hydrogel with NH4+ shows nanotubular morphology with negative surface charge and is used for gel-chromatographic separation of cationic species from anionic counterparts. Furthermore, a photo-responsive luminescent hydrogel is prepared using a cationic tetraphenylethene-based molecular binder (DATPE), which is employed as a light harvesting antenna for tuning emission colour including pure white light. This photo-responsive hydrogel is utilized for writing and preparing flexible light-emitting display.

The coordination polymer is prepared by mixing Zn(OAc) 2 · 2H 2 O (1 m M ) and OPEA (1 m M ) in tetrahydrofuran MOF Nano-Vesicles and Toroids: Self-Assembled Porous Soft-Hybrids for Light Harvesting Metal-organic vesicular and toroid nanostructures of Zn(OPE) · 2H 2 O are achieved by coordination-directed self-assembly of oligo -phenyleneethynylenedicarboxylic acid (OPEA) as a linker with Zn(OAc) 2 by controlling the reaction parameters. Self-assembled nanostructures are characterized by powder X-ray diffraction, fi eld emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and adsorption study. The amphiphilic nature of the coordination-polymer with long alkyl chains renders different soft vesicular and toroidal nanostructures. The permanent porosity of the framework is established by gas adsorption study. Highly luminescent 3D porous framework is exploited for Froster's resonance energy transfer (FRET) by encapsulation of a suitable cationic dye ( DSMP ) which shows effi cient funneling of excitation energy. These results demonstrate the dynamic and soft nature of the MOF, resulting in unprecedented vesicular and toroidal nanostructures with effi cient light harvesting applications.