Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study

Iñigo J. Vitõrica-Yrezábal, Stefano Libri, Jason R. Loader, Guillermo Mínguez Espallargas, Michael Hippler, Ashleigh J. Fletcher, Stephen P. Thompson, John E. Warren, Daniele Musumeci, Michael D. Ward, Lee Brammer

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Despite an absence of conventional porosity, the 1D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10−5 (MeOH), 9.5(3)×10−6 (EtOH), 6.14(5)×10−5 (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH12, in which 2 is the 2D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)2] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-ALT, 1-AHT, 1-BLT and 1-BHT; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH12 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-AHT show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

LanguageEnglish
Pages8799-8811
Number of pages13
JournalChemistry - A European Journal
Volume21
Issue number24
Early online date11 May 2015
DOIs
Publication statusPublished - 28 May 2015

Fingerprint

Thymidine Monophosphate
Polymorphism
Polymers
Vapors
Crystalline materials
Single crystals
Butylated Hydroxytoluene
Die casting inserts
Crystal orientation
X ray powder diffraction
Optical microscopy
Conformations
Infrared spectroscopy
Alcohols
Porosity
Gases
Ligands
Cracks
Temperature
3'-thymidylic acid

Keywords

  • coordination polymers
  • gas-phase spectroscopy
  • in situ diffraction
  • microscopy
  • polymorphism
  • porosity
  • solid-state reactions
  • thermal analysis

Cite this

Vitõrica-Yrezábal, Iñigo J. ; Libri, Stefano ; Loader, Jason R. ; Mínguez Espallargas, Guillermo ; Hippler, Michael ; Fletcher, Ashleigh J. ; Thompson, Stephen P. ; Warren, John E. ; Musumeci, Daniele ; Ward, Michael D. ; Brammer, Lee. / Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction : a multi-technique mechanistic study. In: Chemistry - A European Journal . 2015 ; Vol. 21, No. 24. pp. 8799-8811.
@article{0401afe656164a9f9c1dd8f0de4ce287,
title = "Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study",
abstract = "Despite an absence of conventional porosity, the 1D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10−5 (MeOH), 9.5(3)×10−6 (EtOH), 6.14(5)×10−5 (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH12, in which 2 is the 2D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)2] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-ALT, 1-AHT, 1-BLT and 1-BHT; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH12 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-AHT show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.",
keywords = "coordination polymers, gas-phase spectroscopy, in situ diffraction, microscopy, polymorphism, porosity, solid-state reactions, thermal analysis",
author = "Vit{\~o}rica-Yrez{\'a}bal, {I{\~n}igo J.} and Stefano Libri and Loader, {Jason R.} and {M{\'i}nguez Espallargas}, Guillermo and Michael Hippler and Fletcher, {Ashleigh J.} and Thompson, {Stephen P.} and Warren, {John E.} and Daniele Musumeci and Ward, {Michael D.} and Lee Brammer",
note = "This is the accepted version of the following article: Vit{\~o}rica-Yrez{\'a}bal, I. J., Libri, S., Loader, J. R., M{\'i}nguez Espallargas, G., Hippler, M., Fletcher, A. J., ... Brammer, L. (2015). Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study. Chemistry - A European Journal , 21(24), 8799-8811. which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/chem.201500514/abstract",
year = "2015",
month = "5",
day = "28",
doi = "10.1002/chem.201500514",
language = "English",
volume = "21",
pages = "8799--8811",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
number = "24",

}

Vitõrica-Yrezábal, IJ, Libri, S, Loader, JR, Mínguez Espallargas, G, Hippler, M, Fletcher, AJ, Thompson, SP, Warren, JE, Musumeci, D, Ward, MD & Brammer, L 2015, 'Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study' Chemistry - A European Journal , vol. 21, no. 24, pp. 8799-8811. https://doi.org/10.1002/chem.201500514

Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction : a multi-technique mechanistic study. / Vitõrica-Yrezábal, Iñigo J.; Libri, Stefano; Loader, Jason R.; Mínguez Espallargas, Guillermo; Hippler, Michael; Fletcher, Ashleigh J.; Thompson, Stephen P.; Warren, John E.; Musumeci, Daniele; Ward, Michael D.; Brammer, Lee.

In: Chemistry - A European Journal , Vol. 21, No. 24, 28.05.2015, p. 8799-8811.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction

T2 - Chemistry - A European Journal

AU - Vitõrica-Yrezábal, Iñigo J.

AU - Libri, Stefano

AU - Loader, Jason R.

AU - Mínguez Espallargas, Guillermo

AU - Hippler, Michael

AU - Fletcher, Ashleigh J.

AU - Thompson, Stephen P.

AU - Warren, John E.

AU - Musumeci, Daniele

AU - Ward, Michael D.

AU - Brammer, Lee

N1 - This is the accepted version of the following article: Vitõrica-Yrezábal, I. J., Libri, S., Loader, J. R., Mínguez Espallargas, G., Hippler, M., Fletcher, A. J., ... Brammer, L. (2015). Coordination polymer flexibility leads to polymorphism and enables a crystalline solid-vapour reaction: a multi-technique mechanistic study. Chemistry - A European Journal , 21(24), 8799-8811. which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/chem.201500514/abstract

PY - 2015/5/28

Y1 - 2015/5/28

N2 - Despite an absence of conventional porosity, the 1D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10−5 (MeOH), 9.5(3)×10−6 (EtOH), 6.14(5)×10−5 (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH12, in which 2 is the 2D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)2] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-ALT, 1-AHT, 1-BLT and 1-BHT; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH12 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-AHT show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

AB - Despite an absence of conventional porosity, the 1D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10−5 (MeOH), 9.5(3)×10−6 (EtOH), 6.14(5)×10−5 (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH12, in which 2 is the 2D coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)2] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-ALT, 1-AHT, 1-BLT and 1-BHT; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH12 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-AHT show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

KW - coordination polymers

KW - gas-phase spectroscopy

KW - in situ diffraction

KW - microscopy

KW - polymorphism

KW - porosity

KW - solid-state reactions

KW - thermal analysis

UR - http://www.scopus.com/inward/record.url?scp=84930212727&partnerID=8YFLogxK

U2 - 10.1002/chem.201500514

DO - 10.1002/chem.201500514

M3 - Article

VL - 21

SP - 8799

EP - 8811

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 24

ER -