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Title: Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups

Abstract

The conformational flexibility of three covalently linked alcohol dimers, composed of xanthenol units and diphenyl ether (DPE(OH) 2), 9,9-dimethylxanthene (XAN(OH) 2), or biphenyl (BP(OH) 2) linkers was studied. The relative orientation of the two alcohol units (In-In, In-Out, and Out-Out conformers) in the model compounds was investigated using NMR spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Diols containing rigid linkers, such as XAN(OH) 2 and BP(OH) 2, favor the formation of an In-In conformer in solution, and the interconversion between different conformers was slow on the NMR timescale. Interestingly, XAN(OH) 2 adopted an In-Out conformation in the crystalline solid state, possibly due to additional intermolecular interactions. More flexible DPE(OH) 2 was found to freely interconvert on the NMR timescale. This study provides important structural information that can be utilized in catalysis, metal-ligation, and other applications.

Authors:
 [1];  [1];  [2];  [1]
  1. Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Youngstown State Univ., Youngstown, OH (United States); USDOE
OSTI Identifier:
1582574
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Organic Chemistry
Additional Journal Information:
Journal Volume: 32; Journal Issue: 10; Journal ID: ISSN 1099-1395
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; conformation; conformational analysis; covalently linked dimers; dimer; interconversion

Citation Formats

Zoric, Marija R., Singh, Varun, Zeller, Matthias, and Glusac, Ksenija D. Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups. United States: N. p., 2019. Web. doi:10.1002/poc.3975.
Zoric, Marija R., Singh, Varun, Zeller, Matthias, & Glusac, Ksenija D. Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups. United States. doi:10.1002/poc.3975.
Zoric, Marija R., Singh, Varun, Zeller, Matthias, and Glusac, Ksenija D. Thu . "Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups". United States. doi:10.1002/poc.3975.
@article{osti_1582574,
title = {Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups},
author = {Zoric, Marija R. and Singh, Varun and Zeller, Matthias and Glusac, Ksenija D.},
abstractNote = {The conformational flexibility of three covalently linked alcohol dimers, composed of xanthenol units and diphenyl ether (DPE(OH)2), 9,9-dimethylxanthene (XAN(OH)2), or biphenyl (BP(OH)2) linkers was studied. The relative orientation of the two alcohol units (In-In, In-Out, and Out-Out conformers) in the model compounds was investigated using NMR spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. Diols containing rigid linkers, such as XAN(OH)2 and BP(OH)2, favor the formation of an In-In conformer in solution, and the interconversion between different conformers was slow on the NMR timescale. Interestingly, XAN(OH)2 adopted an In-Out conformation in the crystalline solid state, possibly due to additional intermolecular interactions. More flexible DPE(OH)2 was found to freely interconvert on the NMR timescale. This study provides important structural information that can be utilized in catalysis, metal-ligation, and other applications.},
doi = {10.1002/poc.3975},
journal = {Journal of Physical Organic Chemistry},
number = 10,
volume = 32,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
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    Works referencing / citing this record:

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    journal, January 2004

    • Shimazaki, Yuichi; Nagano, Taro; Takesue, Hironori
    • Angewandte Chemie International Edition, Vol. 43, Issue 1
    • DOI: 10.1002/anie.200352564

    Promoting the Activity of Catalysts for the Oxidation of Water with Bridged Dinuclear Ruthenium Complexes
    journal, February 2013

    • Jiang, Yi; Li, Fei; Zhang, Biaobiao
    • Angewandte Chemie International Edition, Vol. 52, Issue 12
    • DOI: 10.1002/anie.201209045

    1H chemical shifts in NMR: Part 23, the effect of dimethyl sulphoxideversus chloroform solvent on1H chemical shifts
    journal, January 2006

    • Abraham, Raymond J.; Byrne, Jonathan J.; Griffiths, Lee
    • Magnetic Resonance in Chemistry, Vol. 44, Issue 5
    • DOI: 10.1002/mrc.1747

    Pourbaix diagrams in weakly coupled systems: a case study involving acridinol and phenanthridinol pseudobases: POURBAIX DIAGRAMS IN WEAKLY COUPLED SYSTEMS
    journal, December 2015

    • Walpita, Janitha; Yang, Xin; Khatmullin, Renat
    • Journal of Physical Organic Chemistry, Vol. 29, Issue 4
    • DOI: 10.1002/poc.3516

    Conformational flexibility of xanthene-based covalently linked dimers: Xanthene-Based Dimers
    journal, May 2016

    • Zoric, Marija R.; Pandey Kadel, Usha; Korvinson, Kirill A.
    • Journal of Physical Organic Chemistry, Vol. 29, Issue 10
    • DOI: 10.1002/poc.3572

    Crystalline diol hosts featuring a bulky biphenyl framework - Host Synthesis and Formation of Inclusion Compounds
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    • Weber, E.; Wierig, A.; Skobridis, K.
    • Journal f�r Praktische Chemie/Chemiker-Zeitung, Vol. 338, Issue 1
    • DOI: 10.1002/prac.199633801104

    Design of a dinuclear ruthenium based catalyst with a rigid xanthene bridge for catalytic water oxidation
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    Cocatalysis: Role of Organic Cations in Oxygen Evolution Reaction on Oxide Electrodes
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    • Zoric, Marija R.; Kadel, Usha Pandey; Glusac, Ksenija D.
    • ACS Applied Materials & Interfaces, Vol. 10, Issue 32
    • DOI: 10.1021/acsami.8b10232

    The Dynamics of Singlet Fission in Crystalline Tetracene and Covalent Analogs
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    • DOI: 10.1021/cr068079z

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    • Yang, Xin; Walpita, Janitha; Mirzakulova, Ekaterina
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    • DOI: 10.1021/ja01060a068

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    • DOI: 10.1021/jacs.7b13526

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    journal, November 2018

    • Lim, Chern-Hooi; Ilic, Stefan; Alherz, Abdulaziz
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    • DOI: 10.1021/jacs.8b09653

    Triplet State Formation in Photoexcited Slip-Stacked Perylene-3,4:9,10-bis(dicarboximide) Dimers on a Xanthene Scaffold
    journal, September 2013

    • Lefler, Kelly M.; Brown, Kristen E.; Salamant, Walter A.
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    • DOI: 10.1021/jp4083008

    Excited Singlet States of Covalently Bound, Cofacial Dimers and Trimers of Perylene-3,4:9,10-bis(dicarboximide)s
    journal, March 2008

    • Giaimo, Jovan M.; Lockard, Jenny V.; Sinks, Louise E.
    • The Journal of Physical Chemistry A, Vol. 112, Issue 11
    • DOI: 10.1021/jp710847q

    Electrode-assisted catalytic water oxidation by a flavin derivative
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    • Mirzakulova, Ekaterina; Khatmullin, Renat; Walpita, Janitha
    • Nature Chemistry, Vol. 4, Issue 10
    • DOI: 10.1038/nchem.1439

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    1H-NMR as a Structural and Analytical Tool of Intra- and Intermolecular Hydrogen Bonds of Phenol-Containing Natural Products and Model Compounds
    journal, September 2014

    • Charisiadis, Pantelis; Kontogianni, Vassiliki; Tsiafoulis, Constantinos
    • Molecules, Vol. 19, Issue 9
    • DOI: 10.3390/molecules190913643