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61. Sequential Linker Installation: Precise Placement of Functional Groups in Multivariate Metal–Organic Frameworks

Author:
Zhou, Hong-Cai,   et al.   ; Yuan, Shuai; Lu, Weigang; Chen, Ying-Pin; Zhang, Qiang; Liu, Tian-Fu; Feng, Dawei; Wang, Xuan; Qin, Junsheng;     Show all 9 Authors
Source:
Journal of the American Chemical Society 2015 v.137 no.9 pp. 3177-3180
ISSN:
1520-5126
Subject:
X-ray diffraction; coordination polymers; ligands
Abstract:
... A unique strategy, sequential linker installation (SLI), has been developed to construct multivariate MOFs with functional groups precisely positioned. PCN-700, a Zr-MOF with eight-connected Zr₆O₄(OH)₈(H₂O)₄ clusters, has been judiciously designed; the Zr₆ clusters in this MOF are arranged in such a fashion that, by replacement of terminal OH–/H₂O ligands, subsequent insertion of linear dicarboxyl ...
DOI:
10.1021/ja512762r

62. Facile fabrication of cost-effective porous polymer networks for highly selective CO₂ capture

Author:
Zhou, Hong-Cai,   et al.   ; Sun, Lin-Bing; Li, Ai-Guo; Liu, Xiao-Dan; Liu, Xiao-Qin; Feng, Dawei; Lu, Weigang; Yuan, Daqiang;     Show all 8 Authors
Source:
Journal of materials chemistry A 2015 v.3 no.7 pp. 3252-3256
ISSN:
2050-7496
Subject:
Lewis bases; adsorbents; adsorption; carbon; carbon dioxide; catalysts; cost effectiveness; energy efficiency; ethylene; methane; nitrogen; polymerization; polymers; porosity; secondary amines; surfactants; temperature
Abstract:
... Due to their synthetic diversification, low skeletal density, and high physicochemical stability, porous polymer networks (PPNs) are highly promising in a variety of applications such as carbon capture. Nevertheless, complicated monomers and/or expensive catalysts are normally utilized for their synthesis, which makes the process tedious, costly, and hard to scale up. In this study, a facile nucle ...
DOI:
10.1039/c4ta06039c

63. Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area

Author:
Zhou, Hong-Cai,   et al.   ; Liu, Tian-Fu; Feng, Dawei; Chen, Ying-Pin; Zou, Lanfang; Bosch, Mathieu; Yuan, Shuai; Wei, Zhangwen; Fordham, Stephen; Wang, Kecheng;     Show all 10 Authors
Source:
Journal of the American Chemical Society 2015 v.137 no.1 pp. 413-419
ISSN:
1520-5126
Subject:
aqueous solutions; coordination polymers; ligands; pH; porosity; porous media; porphyrins; surface area; topology; zirconium
Abstract:
... Through a topology-guided strategy, a series of Zr₆-containing isoreticular porphyrinic metal–organic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the struc ...
DOI:
10.1021/ja5111317

64. Derivation and Decoration of Nets with Trigonal-Prismatic Nodes: A Unique Route to Reticular Synthesis of Metal–Organic Frameworks

Author:
Zhou, Hong-Cai,   et al.   ; Qin, Jun-Sheng; Du, Dong-Ying; Li, Mian; Lian, Xi-Zhen; Dong, Long-Zhang; Bosch, Mathieu; Su, Zhong-Min; Zhang, Qiang; Li, Shun-Li; Lan, Ya-Qian; Yuan, Shuai;     Show all 12 Authors
Source:
Journal of the American Chemical Society 2016 v.138 no.16 pp. 5299-5307
ISSN:
1520-5126
Subject:
biomimetics; catalysts; catalytic activity; coordination polymers; prediction; topology
Abstract:
... Quests for advanced functionalities in metal–organic frameworks (MOFs) inevitably encounter increasing complexity in their tailored framework architectures, accompanied by heightened challenges with their geometric design. In this paper, we demonstrate the feasibility of rationally exploiting topological prediction as a blueprint for predesigned MOFs. A new triangular frusta secondary building uni ...
DOI:
10.1021/jacs.6b01093

65. Introduction of Functionalized Mesopores to Metal–Organic Frameworks via Metal–Ligand–Fragment Coassembly

Author:
Zhou, Hong-Cai,   et al.   ; Park, Jinhee; Wang, Zhiyong U.; Sun, Lin-Bing; Chen, Ying-Pin;     Show all 5 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.49 pp. 20110-20116
ISSN:
1520-5126
Subject:
catalytic activity; coordination polymers; drugs; ligands; porosity; porous media
Abstract:
... Introduction of functionalized mesopores into microporous metal–organic frameworks (MOFs) can endow them with suitable properties for applications in gas storage, separation, catalysis, and drug delivery. However, common methods for functionalization (including pre- and post-synthetic modifications) of the internal surface of a MOF reduce the pore size of the MOF because the additional functional ...
DOI:
10.1021/ja3085884

66. Interconversion between Discrete and a Chain of Nanocages: Self-Assembly via a Solvent-Driven, Dimension-Augmentation Strategy

Author:
Zhou, Hong-Cai,   et al.   ; Liu, Tian-Fu; Chen, Ying-Pin; Yakovenko, Andrey A.;     Show all 4 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.42 pp. 17358-17361
ISSN:
1520-5126
Subject:
chemical composition; hydrophilicity; hydrophobicity; ligands; solvents
Abstract:
... Using a ligand bearing a bulky hydrophobic group, a “shish kabob” of nanocages, has been assembled through either a one-fell-swoop or a step-by-step procedure by varying the dielectric constant of the assembly mixture. A hydrophobic solvent breaks down the chain to discrete nanocages, while a hydrophilic solvent reverses the procedure. Although the shish kabob of nanocages has exactly the same che ...
DOI:
10.1021/ja306150x

67. Confinement of Metal–Organic Polyhedra in Silica Nanopores

Author:
Zhou, Hong-Cai,   et al.   ; Sun, Lin-Bing; Li, Jian-Rong; Lu, Weigang; Gu, Zhi-Yuan; Luo, Zhiping;     Show all 6 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.38 pp. 15923-15928
ISSN:
1520-5126
Subject:
active sites; adsorption; hydrogen; ligands; nanopores; porous media; silica; thermal stability
Abstract:
... Metal–organic polyhedra (MOPs) have been incorporated into silica nanopores for the first time. Three MOPs with identical geometries but different ligand functionality (namely tert-butyl, hydroxyl, and sulfonic groups) were employed. A typical mesoporous silica, SBA-15, with a two-dimensional hexagonal pore regularity was used as the host. In comparison with bulk MOPs, which prefer to aggregate, M ...
DOI:
10.1021/ja3063925

68. Pore Surface Engineering with Controlled Loadings of Functional Groups via Click Chemistry in Highly Stable Metal–Organic Frameworks

Author:
Zhou, Hong-Cai,   et al.   ; Jiang, Hai-Long; Feng, Dawei; Liu, Tian-Fu; Li, Jian-Rong;     Show all 5 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.36 pp. 14690-14693
ISSN:
1520-5126
Subject:
coordination polymers; crystal structure; dicarboxylic acids; engineering
Abstract:
... Reactions of ZrCl₄ and single or mixed linear dicarboxylic acids bearing methyl or azide groups lead to highly stable isoreticular metal–organic frameworks (MOFs) with content-tunable, accessible, reactive azide groups inside the large pores. These Zr-based MOFs offer an ideal platform for pore surface engineering by anchoring various functional groups with controlled loadings onto the pore walls ...
DOI:
10.1021/ja3063919

69. Cooperative Template-Directed Assembly of Mesoporous Metal–Organic Frameworks

Author:
Zhou, Hong-Cai,   et al.   ; Sun, Lin-Bing; Li, Jian-Rong; Park, Jinhee;     Show all 4 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.1 pp. 126-129
ISSN:
1520-5126
Subject:
cetyltrimethylammonium bromide; chelating agents; citric acid; coordination polymers; micelles; microspores; porous media; surfactants
Abstract:
... Despite great efforts, the development of a reliable way to assemble mesoporous metal–organic frameworks (mesoMOFs) remains a challenge. In this work, we have designed a cooperative template system, comprising a surfactant (cetyltrimethylammonium bromide) and a chelating agent (citric acid), for the generation of a mesoMOF containing a hierarchical system of mesopores interconnected with microspor ...
DOI:
10.1021/ja209698f

70. Reversible Alteration of CO2 Adsorption upon Photochemical or Thermal Treatment in a Metal–Organic Framework

Author:
Zhou, Hong-Cai,   et al.   ; Park, Jinhee; Yuan, Daqiang; Pham, Khanh T.; Li, Jian-Rong; Yakovenko, Andrey;     Show all 6 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.1 pp. 99-102
ISSN:
1520-5126
Subject:
adsorption; carbon dioxide; heat treatment; irradiation
Abstract:
... A metal–organic framework (MOF) for reversible alteration of guest molecule adsorption, here carbon dioxide, upon photochemical or thermal treatment has been discovered. An azobenzene functional group, which can switch its conformation upon light irradiation or heat treatment, has been introduced to the organic linker of a MOF. The resulting MOF adsorbs different amount of CO₂ after UV or heat tre ...
DOI:
10.1021/ja209197f

71. An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence

Author:
Zhou, Hong-Cai,   et al.   ; Jiang, Hai-Long; Feng, Dawei; Wang, Kecheng; Gu, Zhi-Yuan; Wei, Zhangwen; Chen, Ying-Pin;     Show all 7 Authors
Source:
Journal of the American Chemical Society 2013 v.135 no.37 pp. 13934-13938
ISSN:
1520-5126
Subject:
aqueous solutions; boiling; fluorescence; organic compounds; pH; zirconium
Abstract:
... A reaction between a Zrᴵⱽ salt and a porphyrinic tetracarboxylic acid leads to a metal–organic framework (MOF) with two types of open channels, representing a MOF featuring a (4,8)-connected sqc net. The MOF remains intact in both boiling water and aqueous solutions with pH ranging from 1 to 11, a remarkably extensive pH range that a MOF can sustain. Given its exceptional stability and pH-dependen ...
DOI:
10.1021/ja406844r

72. Reversible Switching from Antiferro- to Ferromagnetic Behavior by Solvent-Mediated, Thermally-Induced Phase Transitions in a Trimorphic MOF-Based Magnetic Sponge System

Author:
Zhou, Hong-Cai,   et al.   ; Wriedt, Mario; Yakovenko, Andrey A.; Halder, Gregory J.; Prosvirin, Andrey V.; Dunbar, Kim R.;     Show all 6 Authors
Source:
Journal of the American Chemical Society 2013 v.135 no.10 pp. 4040-4050
ISSN:
1520-5126
Subject:
X-ray diffraction; acetates; copper; differential scanning calorimetry; ferrimagnetic materials; heat; helium; ligands; magnetic properties; phase transition; propane; spectral analysis; streams; thermal properties; thermogravimetry
Abstract:
... Hydrothermal reactions of copper(II) acetate, tetrazolate-5-carboxylate (tzc), and the neutral N-donor spacer ligand 1,3-di(4-pyridyl)propane (dpp) lead in a single reaction vial to the simultaneous formation of three different single-crystalline solvates [Cu(tzc)(dpp)]ₙ·0.5C₆H₁₄·0.5H₂O (1), [Cu(tzc)(dpp)]ₙ·4.5H₂O (2), and [Cu(tzc)(dpp)]ₙ·1.25C₆H₁₄ (3). All three structures were characterized by s ...
DOI:
10.1021/ja312347p

73. A Highly Stable Porphyrinic Zirconium Metal–Organic Framework with shp-a Topology

Author:
Zhou, Hong-Cai,   et al.   ; Feng, Dawei; Gu, Zhi-Yuan; Chen, Ying-Pin; Park, Jihye; Wei, Zhangwen; Sun, Yujia; Bosch, Mathieu; Yuan, Shuai;     Show all 9 Authors
Source:
Journal of the American Chemical Society 2014 v.136 no.51 pp. 17714-17717
ISSN:
1520-5126
Subject:
aqueous solutions; catalysts; iron; pH; topology; zirconium
Abstract:
... Through a kinetically controlled synthetic process, we synthesized PCN-223, a new porphyrinic Zr-MOF constructed from the newly reported hexagonal prismatic 12-connected Zr₆ cluster through an unusual disordered arrangement, giving rise to the first example of the shp-a network in MOFs. With its extremely high connectivity, PCN-223 shows high stability in aqueous solutions with a wide range of pH. ...
DOI:
10.1021/ja510525s

74. A Series of Highly Stable Mesoporous Metalloporphyrin Fe-MOFs

Author:
Zhou, Hong-Cai,   et al.   ; Wang, Kecheng; Feng, Dawei; Liu, Tian-Fu; Su, Jie; Yuan, Shuai; Chen, Ying-Pin; Bosch, Mathieu; Zou, Xiaodong;     Show all 9 Authors
Source:
Journal of the American Chemical Society 2014 v.136 no.40 pp. 13983-13986
ISSN:
1520-5126
Subject:
aqueous solutions; cobalt; copper; iron; manganese; nickel; pH; peroxidase; porous media
Abstract:
... A series of mesoporous metalloporphyrin Fe-MOFs, namely PCN-600(M) (M = Mn, Fe, Co, Ni, Cu), have been synthesized using the preassembled [Fe₃O(OOCCH₃)₆] building block. PCN-600 exhibits a one-dimensional channel as large as 3.1 nm and the highest experimental pore volume of 1.80 cm³g–¹ among all the reported porphyrinic MOFs. It also shows very high stability in aqueous solutions with pH values r ...
DOI:
10.1021/ja507269n

75. Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

Author:
Zhou, Hong-Cai,   et al.   ; Wei, Zhangwen; Gu, Zhi-Yuan; Arvapally, Ravi K.; Chen, Ying-Pin; McDougald, Roy N.; Ivy, Joshua F.; Yakovenko, Andrey A.; Feng, Dawei; Omary, Mohammad A.;     Show all 10 Authors
Source:
Journal of the American Chemical Society 2014 v.136 no.23 pp. 8269-8276
ISSN:
1520-5126
Subject:
ambient temperature; coordination polymers; energy; fluorescence; photoluminescence; zirconium
Abstract:
... We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal–organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.5%) under Ar, rep ...
DOI:
10.1021/ja5006866

76. Ultrastable Polymolybdate-Based Metal–Organic Frameworks as Highly Active Electrocatalysts for Hydrogen Generation from Water

Author:
Zhou, Hong-Cai,   et al.   ; Qin, Jun-Sheng; Du, Dong-Ying; Guan, Wei; Bo, Xiang-Jie; Li, Ya-Fei; Guo, Li-Ping; Su, Zhong-Min; Wang, Yuan-Yuan; Lan, Ya-Qian;     Show all 10 Authors
Source:
Journal of the American Chemical Society 2015 v.137 no.22 pp. 7169-7177
ISSN:
1520-5126
Subject:
air; cathodes; coordination polymers; electrolytes; hydrogen production; ions; ligands; porosity; tetrabutylammonium compounds
Abstract:
... Two novel polyoxometalate (POM)-based metal–organic frameworks (MOFs), [TBA]₃[ε-PMoⱽ₈Moⱽᴵ₄O₃₆(OH)₄Zn₄][BTB]₄/₃·xGuest (NENU-500, BTB = benzene tribenzoate, TBA⁺ = tetrabutylammonium ion) and [TBA]₃[ε-PMoⱽ₈Moⱽᴵ₄O₃₇(OH)₃Zn₄][BPT] (NENU-501, BPT = [1,1′-biphenyl]-3,4′,5-tricarboxylate), were isolated. In these compounds, the POM fragments serving as nodes were directly connected with organic ligands ...
DOI:
10.1021/jacs.5b02688

77. Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination

Author:
Zhou, Hong-Cai,   et al.   ; Feng, Dawei; Chung, Wan-Chun; Wei, Zhangwen; Gu, Zhi-Yuan; Jiang, Hai-Long; Chen, Ying-Pin; Darensbourg, Donald J.;     Show all 8 Authors
Source:
Journal of the American Chemical Society 2013 v.135 no.45 pp. 17105-17110
ISSN:
1520-5126
Subject:
aqueous solutions; catalysts; catalytic activity; cobalt; coordination polymers; iron; nickel; pH; porphyrins; surface area; zirconium
Abstract:
... A series of highly stable MOFs with 3-D nanochannels, namely PCN-224 (no metal, Ni, Co, Fe), have been assembled with six-connected Zr₆ cluster and metalloporphyrins by a linker-elimination strategy. The PCN-224 series not only exhibits the highest BET surface area (2600m²/g) among all the reported porphyrinic MOFs but also remains intact in pH = 0 to pH = 11 aqueous solution. Remarkably, PCN-224( ...
DOI:
10.1021/ja408084j

78. Multipoint Interactions Enhanced CO2 Uptake: A Zeolite-like Zinc–Tetrazole Framework with 24-Nuclear Zinc Cages

Author:
Zhou, Hong-Cai,   et al.   ; Cui, Ping; Ma, Yu-Guang; Li, Huan-Huan; Zhao, Bin; Li, Jian-Rong; Cheng, Peng; Balbuena, Perla B.;     Show all 8 Authors
Source:
Journal of the American Chemical Society 2012 v.134 no.46 pp. 18892-18895
ISSN:
1520-5126
Subject:
adsorption; carbon dioxide; organic compounds; porous media; zeolites; zinc
Abstract:
... A zeolite-like microporous tetrazole-based metal–organic framework (MOF) with 24 nuclear zinc cages was synthesized and characterized. It exhibits high CO₂ adsorption capacity up to 35.6 wt % (8.09 mmol/g) and excellent CO₂/CH₄ selectivity at 273 K/1 bar, being among the highest values known to date. Theoretical calculations based on simulated annealing techniques and periodic DFT revealed that CO ...
DOI:
10.1021/ja3063138

79. Temperature-dependent supramolecular stereoisomerism in porous copper coordination networks based on a designed carboxylate ligand

Author:
Zhou, Hong-Cai,   et al.   ; Sun, Daofeng; Ke, Yanxiong; Mattox, Tracy M.; Ooro, Betty A.;     Show all 5 Authors
Source:
Chemical communications 2005 no.43 pp. 5447-5449
ISSN:
1364-548X
Subject:
copper; ligands; stereoisomerism; stereoisomers
Abstract:
... Two novel temperature-controlled supramolecular stereoisomers of porous copper coordination networks have been synthesized and characterized. ...
DOI:
10.1039/b505664k