Designer coordination polymers: dimensional crossover architectures and proton conduction

Abstract

Coordination polymers (CPs) have large degrees of freedom in framework compositions and in the structures and environment of the inner pores. This review focuses on the recent significant progress achieved by controlling these degrees of freedom. Two breakthroughs are reviewed for constructing sophisticated structures of CP frameworks, especially in dimensional crossover regions. The first is the synthesis of quasi one-dimensional halogen-bridged coordinative tubes by applying state-of-the-art techniques of coordination chemistry. The electronic state of the coordinative tube was studied by structural, spectroscopic and theoretical methods and found to be distinct from conventional one-dimensional systems. The second breakthrough is the achievement of a quasi-two-dimensional architecture by combining Langmuir-Blodgett and layer-by-layer methods. Two-dimensional LB CP films were prepared on liquid; the films were stacked layer by layer, and a crystalline quasi-two-dimensional structure was constructed. This review also covers the design of the environment of the inner pore, where hydrogen bond networks with various acidic sites were modified. By appropriate design of the hydrogen bond network, proton-conductive CPs are invented, which are summarized in this review. Types of proton donor sites are discussed and classified, and superprotonic conductive CPs were achieved in these investigations. These results will provide new strategies for constructing functional materials for smart devices.

Water Structure and Dynamics in Homochiral [Zn(l-L)(X)] Metal–Organic Frameworks

“…The intrinsic chemical diversity and porosity make metal-organic frameworks (MOFs) promising materials for several technological applications, including gas storage (e.g., methane and hydrogen storage), 1-11 carbon capture, [12][13][14][15][16][17] hydrocarbon separation, [18][19][20] catalysis, [21][22][23][24][25][26][27] electrical [28][29] and proton [30][31][32][33][34][35][36][37][38][39][40][41][42] conductivity, magnetism [43][44][45][46][47][48] and luminescence. 49 However, despite their versatility, several frameworks display low stability when exposed to moisture, which has limited the use of MOFs in industrial applications thus far.…”

Exploitation of Guest Accessible Aliphatic Amine Functionality of a Metal–Organic Framework for Selective Detection of 2,4,6-Trinitrophenol (TNP) in Water

“…32,35,[52][53][54][55][56] In this regard, instead of solubilization of the probe, water-stability is a unique feature exhibited by some of the new-generation functional materials like metal-organic frameworks (MOFs); [57][58][59][60] wherein the inherent porous franework remains unaffected in water, even after prolonged exposure for the specific waterstable MOFs. Apart from their well-recognized multifarious applications in the microporous domain; [61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78] MOFs have established themselves as excellent sensory materials because of the unmatched combination of crystallinity, permanent porosity, and designable pores with tailored window-sizes, systematically tunable band gaps and electronic structures. [79][80][81][82][83][84][85] In general, favourable interactions between target analyte and MOF backbone result into the observed PL-sensing performance for MOFs.…”

Immobilization of Cu Complex into Zr-Based MOF with Bipyridine Units for Heterogeneous Selective Oxidation

“…In this line, metal−organic frameworks (MOFs), also called porous coordination polymers (PCPs), have attracted much attention to utilize their various unique features such as high 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 specific surface areas, ordered porous structures and structure designability. [13][14][15][16][17][18][19][20][21] MOFs have provided a highly tunable platform for designing single-site solid catalysts for a variety of catalytic reactions. [22][23][24][25][26][27][28][29] Unlike traditional inorganic porous materials, unlimited possible combinations of metal-oxo clusters and organic linkers allow access to reticular structures with tunable pore sizes and functional properties.…”