Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

Witold M. Bloch; Alexandre Burgun; Campbell J. Coghlan; Richmond Lee; Michelle L. Coote; Christian J. Doonan; Christopher J. Sumby

doi:10.1038/nchem.2045

Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

Witold M. Bloch, Alexandre Burgun, Campbell J. Coghlan, Richmond Lee, Michelle L. Coote, Christian J. Doonan, Christopher J. Sumby^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

177 Citations (Scopus)

Abstract

Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)₂[[Rh(CO)₂ Cl₂[.

Original language	English
Pages (from-to)	906-912
Number of pages	7
Journal	Nature Chemistry
Volume	6
Issue number	10
DOIs	https://doi.org/10.1038/nchem.2045
Publication status	Published - 1 Oct 2014

Access to Document

10.1038/nchem.2045

Cite this

@article{71beef1df8a74b2984b15ab47177a263,

title = "Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks",

abstract = "Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2[[Rh(CO)2 Cl2[.",

author = "Bloch, {Witold M.} and Alexandre Burgun and Coghlan, {Campbell J.} and Richmond Lee and Coote, {Michelle L.} and Doonan, {Christian J.} and Sumby, {Christopher J.}",

year = "2014",

month = oct,

day = "1",

doi = "10.1038/nchem.2045",

language = "English",

volume = "6",

pages = "906--912",

journal = "Nature Chemistry",

issn = "1755-4330",

publisher = "Nature Publishing Group",

number = "10",

}

TY - JOUR

T1 - Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

AU - Bloch, Witold M.

AU - Burgun, Alexandre

AU - Coghlan, Campbell J.

AU - Lee, Richmond

AU - Coote, Michelle L.

AU - Doonan, Christian J.

AU - Sumby, Christopher J.

PY - 2014/10/1

Y1 - 2014/10/1

N2 - Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2[[Rh(CO)2 Cl2[.

AB - Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2[[Rh(CO)2 Cl2[.

UR - http://www.scopus.com/inward/record.url?scp=84940822472&partnerID=8YFLogxK

U2 - 10.1038/nchem.2045

DO - 10.1038/nchem.2045

M3 - Article

SN - 1755-4330

VL - 6

SP - 906

EP - 912

JO - Nature Chemistry

JF - Nature Chemistry

IS - 10

ER -

Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

Abstract

Access to Document

Other files and links

Fingerprint

Cite this