Chen Shao-Li    Yang Zi Run    Wang Bin Jie    Shang Yu    Sun Lin-Ying    Chunting He    Zhou Hao-Long    Weixiong Zhang    陈小明    

Science China Materials

2018

Among various types of nonporous and porous coordination polymers, and as a subset of metal azolate frameworks (MAFs), Cu(I) 1,2,4-triazolates are unique for their simple three-connected network topologies which can be controlled by their significant steric hindrance effects between the noncoordinative side groups. This perspective article discusses the crystal engineering, structures, and diversified properties of Cu(I) 1,2,4-triazolates, particularly focusing on the porous coordination polymer [Cu(detz)] (MAF-2, Hdetz = 3,5-diethyl-1,2,4-triazole) showing unique/multimode flexibility, high hydrophobicity, bright phosphorescence, and exceptionally high stabilities toward not only guest change but also water and oxygen, which have demonstrated as a good platform for realizing high-performance applications related to gas/vapor confinement, storage, separation, and sensing. The exceptional O reactivity and the tunable framework flexibility, pore surface polarity, and gas separation performances of [Cu(btm)] (MAF-42, Hbtm = bis(5-methyl-1,2,4-triazol-3-yl)methane) are also summarized.

Liu Si-Yang    Jiepeng Zhang    陈小明    

Crystal Growth and Design

2017

The construction of metal-organic frameworks (MOFs) by mixed-bridging organic ligands represents an important and widely used strategy for the design and synthesis of MOFs with a higher level of complexity, which shows advantages in the discovery of new topologies, multiple-step self-assembly, and anisotropic modification on pore sizes and shapes. This article summarizes important advances in MOFs with mixed-bridging organic ligands, covering the design and synthetic methods, structures, and properties.

Minghua Zeng    陈小明    

Comprehensive Supramolecular Chemistry II

2017

Porous materials capable of selectively capturing COfrom flue-gases or natural gas are of interest in terms of rising atmospheric COlevels and methane purification. Size-exclusive sieving of COover CHand Nhas rarely been achieved. Herein we show that a crystal engineering approach to tuning of pore-size in a coordination network, [Cu(quinoline-5-carboxyate)](Qc-5-Cu) ena+bles ultra-high selectivity for COover N(S≈40 000) and CH(S≈3300). Qc-5-Cu-sql-β, a narrow pore polymorph of the square lattice (sql) coordination network Qc-5-Cu-sql-α, adsorbs COwhile excluding both CHand N. Experimental measurements and molecular modeling validate and explain the performance. Qc-5-Cu-sql-β is stable to moisture and its separation performance is unaffected by humidity.

Kaijie Chen    David Madden    Tony Pham    Katherine Forrest    Amrit Kumar    Qingyuan Yang    Xue Wei    Brian Space    Perry Iv John J.    Jiepeng Zhang    陈小明     Michael Zaworotko   

Angewandte Chemie - International Edition

2016

By using pyridyl derivatives 4-cyanopyridine (4-pyCN) or nicotinate (na) as terminal ligands (L) to decorate the flexible trigonal-prismatic trinuclear metal carboxylate M(μ-O/μ-OH)(RCOO)(L) clusters, a theoretically predicted uninodal 6-connected flu-e network for [M(μ-O/μ-OH)(bdc)(L)] (Hbdc = 1,4-benzenedicarboxylic acid) has been realized in three new porous coordination frameworks. The flu-e topology is isomeric to the uninodal 6-connected acs (MIL-88) and tetranodal 6-connected mtn-e (MIL-101) ones observed in the classic metal carboxylate framework materials, but comprises of unique cubic cages which require exceptional conformation for the trinuclear clusters. The weak coordinating 4-pyCN terminal ligands tend to leave the clusters during thermal activation, leading to framework distortion and reduction of the long-range order of the flu-e network, which can only be restored by 4-pyCN instead of other guest molecules. On the other hand, the carboxylate ends of the adjacent na ligands coordinate with additional metal ions to crosslink the coordination networks as new binodal 4,9-connected networks with remarkably enhanced thermal/chemical stability and porosity.

Wei Yong-Sheng    Shen Jian-Qiang    聊培钦    Xue Wei    Jiepeng Zhang    陈小明    

Dalton Transactions

2016

The first thiocyanate-bridged double perovskite-type coordination polymer [NH][NiCd(SCN)] is reported here, which undergoes a reversible structural phase transition at around 120 K. An order-disorder mechanism for this transition is disclosed by X-ray structural analyses, dielectric measurement, as well as molecular dynamics simulations.

Xie Kai-Ping    Xu Wei-Jian    Chunting He    Huang Bo    Ziyi Du    Su Yu-Jun    Weixiong Zhang    陈小明    

CrystEngComm

2016

Nanosized aggregations of metal ions shielded by organic ligands possessing both exquisite structural aesthetics and intriguing properties are fundamentally interesting. Three isostructural gigantic transition-metal–rare-earth heterometallic coordination cages are reported, abbreviated as {NiRE} (RE=Gd, Dy, and Y) and obtained by a mixed-ligand approach, each possessing a cuboidal framework made of 160 metal ions and a nanosized spherical cavity in the center. Along with the structural novelty, these hollow cages show highly selective adsorptions for COover CHor Nat ambient temperatures. Moreover, the gadolinium analogue exhibits large magnetocaloric effect at ultralow temperatures.

Chen Wei-Peng    聊培钦    Yu Youzhu    郑智平    陈小明     Zheng Yan-Zhen   

Angewandte Chemie - International Edition

2016

A series of highly connected metal–organic frameworks (MOFs), [Co(O)(OH)(HO)(ina)](NO)⋅2 CHOH⋅4 HO (1), [Co(O)(OH)(HO)(pba)](NO)⋅8 CHOH⋅28 HO (2), and [Co(O)(OH)(HO)(pbba)](NO)⋅guest (3), in which ina=isonicotinate, pba=4-pyridylbenzoate, and pbba=4-(pyridine-4-yl)phenylbenzoate, is reported. These MOFs contain a new secondary building unit (SBU), with a square Co(μ-O) central unit having the rare μ-Omotif, which is decorated by the other four peripheral cobalt atoms through μ-OH in a windmill-like shape. This SBU holds 16 divergent connecting organic ligands, pyridyl-carboxylates, to form three different frameworks. The high porosity of desolvated 2 is shown by the efficient gas absorption of N, CO, CH, and H. In addition, 1 and 2 exhibit unusual canted antiferromagnetic behavior with spin-glass-like relaxation, with blocking temperatures that are fairly high, 20 K (1) and 10 K (2), for cobalt materials. The relationship between the metal clusters and linkers has been studied, in which the size and rotational degrees of freedom of the ligands are found to control the topology, gas sorption, and magnetic properties.

Chen Qing    Xue Wei    Jianbin Lin    Wei Yong-Sheng    Zheng Yin    Minghua Zeng    Mohamedally Kurmoo    陈小明    

Chemistry - A European Journal

2016

Xu Wei-Jian    Chunting He    Chengmin Ji    Chen Shao-Li    Huang Rui-Kang    Lin Rui-Biao    Xue Wei    Luo Junhua    Weixiong Zhang    陈小明    

Advanced Materials

2016

Chen Qing    Xue Wei    Jianbin Lin    Wei Yong-Sheng    Zheng Yin    Minghua Zeng    Mohamedally Kurmoo    陈小明    

Chemistry - A European Journal

2016