Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

2016 ◽  
Vol 138 (31) ◽  
pp. 9783-9786 ◽  
Author(s):  
Takahiro Sawano ◽  
Zekai Lin ◽  
Dean Boures ◽  
Bing An ◽  
Cheng Wang ◽  
...  
Keyword(s):  
Metal Complexes ◽  
Metal Organic Frameworks ◽  
Catalytic Reactions ◽  
Broad Scope ◽  
Metal Organic

scholarly journals X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

2017 ◽  
Vol 375 (2084) ◽  
pp. 20160028 ◽  
Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Metal Organic Frameworks ◽  
Void Space ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Nitrates ◽  
Metal Organic

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

scholarly journals Host-Guest Interactions Between Metal–Organic Frameworks and Air-Sensitive Complexes at High Temperature

2021 ◽  
Vol 9 ◽  
Author(s):  
Bo Huang ◽  
Zhe Tan
Keyword(s):  
High Temperature ◽  
Metal Complexes ◽  
High Temperatures ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Chemical Vapor ◽  
Chemical Vapor Infiltration ◽  
Synthetic Methods ◽  
Infiltration Process ◽  
Metal Organic

The host-guest chemistry of metal–organic frameworks (MOFs) has been attracting increasing attention owing to the outstanding properties derived from MOFs-guests combinations. However, there are large difficulties involved in the syntheses of the host-guest MOF systems with air-sensitive metal complexes. In addition, the behaviors on host-guest interactions in the above systems at high temperature are not clear. This study reported the synthetic methods for host-guest systems of metal–organic framework and air-sensitive metal complexes via a developed chemical vapor infiltration process. With the synchrotron X-ray powder diffraction (XRPD) measurements and Fourier Transform infrared spectroscopy (FTIR), the successful loadings of Fe(CO)5 in HKUST-1 and NH2-MIL-101(Al) have been confirmed. At high temperatures, the structural and chemical componential changes were investigated in detail by XRPD and FTIR measurements. HKUST-1 was proven to have strong interaction with Fe(CO)5 and resulted in a heavy loading amount of 63.1 wt%, but too strong an interaction led to deformation of HKUST-1 sub-unit under heating conditions. NH2-MIL-101(Al), meanwhile, has a weaker interaction and is chemically inert to Fe(CO)5 at high temperatures.

scholarly journals Functionalising metal–organic frameworks with metal complexes: the role of structural dynamics

CrystEngComm ◽  
2015 ◽  
Vol 17 (40) ◽  
pp. 7632-7635 ◽  
Author(s):  
Ana E. Platero-Prats ◽  
Antonio Bermejo Gómez ◽  
Karena W. Chapman ◽  
Belén Martín-Matute ◽  
Xiaodong Zou
Keyword(s):  
Metal Complexes ◽  
Structural Dynamics ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Metal Organic ◽  
The Impact ◽  
Organic Framework

The impact of dynamics in the functionalisation of metal–organic framework UiO-67 with an Ir-complex has been studied. Highly functionalised Ir-UiO-67 can be only trapped as kinetic products, which lose metals and exchange species to gain stability.

scholarly journals Lower Activation Energy for Catalytic Reactions through Host-Guest Cooperation within Metal-Organic Frameworks

2018 ◽  
Vol 130 (32) ◽  
pp. 10264-10268 ◽  
Author(s):  
Briana Aguila ◽  
Qi Sun ◽  
Xiaoliang Wang ◽  
Erica O'Rourke ◽  
Abdullah M. Al-Enizi ◽  
...  
Keyword(s):  
Activation Energy ◽  
Metal Organic Frameworks ◽  
Catalytic Reactions ◽  
Lower Activation ◽  
Metal Organic ◽  
Lower Activation Energy

scholarly journals The First One-Pot Synthesis of Metal-Organic Frameworks Functionalised with Two Transition-Metal Complexes

2014 ◽  
Vol 21 (2) ◽  
pp. 861-866 ◽  
Author(s):  
Ana E. Platero-Prats ◽  
Antonio Bermejo Gómez ◽  
Louise Samain ◽  
Xiaodong Zou ◽  
Belén Martín-Matute
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Metal Organic Frameworks ◽  
One Pot ◽  
One Pot Synthesis ◽  
Metal Organic

Privileged Phosphine-Based Metal–Organic Frameworks for Broad-Scope Asymmetric Catalysis

2014 ◽  
Vol 136 (14) ◽  
pp. 5213-5216 ◽  
Author(s):  
Joseph M. Falkowski ◽  
Takahiro Sawano ◽  
Teng Zhang ◽  
Galen Tsun ◽  
Yuan Chen ◽  
...  
Keyword(s):  
Asymmetric Catalysis ◽  
Metal Organic Frameworks ◽  
Broad Scope ◽  
Metal Organic

Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks

2017 ◽  
Vol 46 (11) ◽  
pp. 3431-3452 ◽  
Author(s):  
Hala Assi ◽  
Georges Mouchaham ◽  
Nathalie Steunou ◽  
Thomas Devic ◽  
Christian Serre
Keyword(s):  
Metal Complexes ◽  
Coordination Compounds ◽  
Metal Organic Frameworks ◽  
Recent Advances ◽  
Metal Organic ◽  
Molecular Compounds

Recent advances in titanium based MOFs and relevant titanium molecular compounds will be discussed in this review. Particular attention will be devoted to their promising photoredox properties.

scholarly journals Pore-controlled formation of 0D metal complexes in anionic 3D metal–organic frameworks

CrystEngComm ◽  
2015 ◽  
Vol 17 (5) ◽  
pp. 996-1000 ◽  
Author(s):  
Muwei Zhang ◽  
Mathieu Bosch ◽  
Hong-Cai Zhou
Keyword(s):  
Metal Complexes ◽  
Single Crystal ◽  
Metal Organic Frameworks ◽  
Single Crystal Xrd ◽  
Metal Organic ◽  
Guest Chemistry

The host–guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD.

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