Gold-Clip-Assisted Self-Assembly and Proton-Coupled Expansion–Contraction of a Cofacial FeIII–Porphyrin Cage

Yuanyuan Wang; Pau Lin Ang; Chun-Yuen Wong; John H. K. Yip

doi:10.1002/chem.201803501

Gold-Clip-Assisted Self-Assembly and Proton-Coupled Expansion–Contraction of a Cofacial Fe^III–Porphyrin Cage

Yuanyuan Wang
, Pau Lin Ang
, Chun-Yuen Wong
, John H. K. Yip^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

11 Citations (Scopus)

Abstract

A molecular cage {Au₈(μ-PAnP)₄[Fe(H₂O)₂(TPyP)]₂(OTf)₂}(OTf)₈ (1) composed of two cofacial Fe^III-porphyrin can be self-assembled from the gold clip [Au₂(PAnP)Cl₂] and Fe³⁺(H₂O)₂(TPyP)⁺ (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) Å. The addition of a base to a solution of the cage leads to a contracted and twisted cage {[Au₈(μ-PAnP)₄[Fe₂(μ-O)(TPyP)₂]}(OTf)₈ (2), which has a height of ≈4.4 Å and porphyrin–porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe₂(μ-O)(TPyP)₂. The spectroscopy and crystal structure of an unclipped analog of the contracted cage, {[AuPPh₃)₈[Fe₂(μ-O)(TPyP)₂]}(OTf)₈ (3), supports the DFT-calculated structure of 2. NMR and UV/Vis titrations show that the expansion-untwisting and contraction-twisting of the cage is reversible.

Original language	English
Pages (from-to)	18623-18628
Journal	Chemistry - A European Journal
Volume	24
Issue number	70
Online published	15 Sept 2018
DOIs	https://doi.org/10.1002/chem.201803501
Publication status	Published - 12 Dec 2018

Research Keywords

cage compounds
gold
molecular machines
self-assembly
supramolecular chemistry

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@article{c9913df5a0454bf9a8ce685aee08b873,

title = "Gold-Clip-Assisted Self-Assembly and Proton-Coupled Expansion–Contraction of a Cofacial FeIII–Porphyrin Cage",

abstract = "A molecular cage \{Au8(μ-PAnP)4[Fe(H2O)2(TPyP)]2(OTf)2\}(OTf)8 (1) composed of two cofacial FeIII-porphyrin can be self-assembled from the gold clip [Au2(PAnP)Cl2] and Fe3+(H2O)2(TPyP)+ (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) {\AA}. The addition of a base to a solution of the cage leads to a contracted and twisted cage \{[Au8(μ-PAnP)4[Fe2(μ-O)(TPyP)2]\}(OTf)8 (2), which has a height of ≈4.4 {\AA} and porphyrin–porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe2(μ-O)(TPyP)2. The spectroscopy and crystal structure of an unclipped analog of the contracted cage, \{[AuPPh3)8[Fe2(μ-O)(TPyP)2]\}(OTf)8 (3), supports the DFT-calculated structure of 2. NMR and UV/Vis titrations show that the expansion-untwisting and contraction-twisting of the cage is reversible.",

keywords = "cage compounds, gold, molecular machines, self-assembly, supramolecular chemistry",

author = "Yuanyuan Wang and Ang, \{Pau Lin\} and Chun-Yuen Wong and Yip, \{John H. K.\}",

year = "2018",

month = dec,

day = "12",

doi = "10.1002/chem.201803501",

language = "English",

volume = "24",

pages = "18623--18628",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons",

number = "70",

}

TY - JOUR

T1 - Gold-Clip-Assisted Self-Assembly and Proton-Coupled Expansion–Contraction of a Cofacial FeIII–Porphyrin Cage

AU - Wang, Yuanyuan

AU - Ang, Pau Lin

AU - Wong, Chun-Yuen

AU - Yip, John H. K.

PY - 2018/12/12

Y1 - 2018/12/12

N2 - A molecular cage {Au8(μ-PAnP)4[Fe(H2O)2(TPyP)]2(OTf)2}(OTf)8 (1) composed of two cofacial FeIII-porphyrin can be self-assembled from the gold clip [Au2(PAnP)Cl2] and Fe3+(H2O)2(TPyP)+ (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) Å. The addition of a base to a solution of the cage leads to a contracted and twisted cage {[Au8(μ-PAnP)4[Fe2(μ-O)(TPyP)2]}(OTf)8 (2), which has a height of ≈4.4 Å and porphyrin–porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe2(μ-O)(TPyP)2. The spectroscopy and crystal structure of an unclipped analog of the contracted cage, {[AuPPh3)8[Fe2(μ-O)(TPyP)2]}(OTf)8 (3), supports the DFT-calculated structure of 2. NMR and UV/Vis titrations show that the expansion-untwisting and contraction-twisting of the cage is reversible.

AB - A molecular cage {Au8(μ-PAnP)4[Fe(H2O)2(TPyP)]2(OTf)2}(OTf)8 (1) composed of two cofacial FeIII-porphyrin can be self-assembled from the gold clip [Au2(PAnP)Cl2] and Fe3+(H2O)2(TPyP)+ (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) Å. The addition of a base to a solution of the cage leads to a contracted and twisted cage {[Au8(μ-PAnP)4[Fe2(μ-O)(TPyP)2]}(OTf)8 (2), which has a height of ≈4.4 Å and porphyrin–porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe2(μ-O)(TPyP)2. The spectroscopy and crystal structure of an unclipped analog of the contracted cage, {[AuPPh3)8[Fe2(μ-O)(TPyP)2]}(OTf)8 (3), supports the DFT-calculated structure of 2. NMR and UV/Vis titrations show that the expansion-untwisting and contraction-twisting of the cage is reversible.

KW - cage compounds

KW - gold

KW - molecular machines

KW - self-assembly

KW - supramolecular chemistry

UR - https://www.scopus.com/pages/publications/85056392246

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85056392246&origin=recordpage

U2 - 10.1002/chem.201803501

DO - 10.1002/chem.201803501

M3 - RGC 21 - Publication in refereed journal

SN - 0947-6539

VL - 24

SP - 18623

EP - 18628

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 70

ER -