Stimuli-Responsive Self-Assembly and Spatial Functionalization of Organic Cages Based on ...

160 Pages·2017·17.35 MB·English

Stimuli-Responsive Self-Assembly and
Spatial Functionalization of
Organic Cages Based on
Tribenzotriquinacenes

Dissertation zur Erlangung des
naturwissenschaftlichen Doktorgrades
der Julius-Maximilians-Universität Würzburg

vorgelegt von
Ayan Dhara
aus Singarkone, Indien

Würzburg 2017

Eingereicht bei der Fakultät für Chemie und Pharmazie am:
__11_._0_9_.2_0_1_7___________

Gutachter der schriftlichen Arbeit:
1. Gutachter: Priv.-Doz. Dr. Florian Beuerle
2. Gutachter: Prof. Dr. Frank Würthner

Prüfer des öffentlichen Promotionskolloquiums:
1. Prüfer: Priv.-Doz. Dr. Florian Beuerle
2. Prüfer: Prof. Dr. Frank Würthner
3. Prüfer:
Prof. Dr. Udo Radius

Datum des öffentlichen Promotionskolloquiums:
_2_7_._10_._2_0_17____________

Doktorurkunde ausgehändigt am:
____________________

i
ii
Dedicated
To
My beloved
Parents

iii
iv
List of Abbreviations

BARF Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate
BET Brunauer-Emmett-Teller
CCDC Cambridge Crystallographic Data Center
COF Covalent Organic Framework
CTV Cyclotriveratrylene
D Diffusion Coefficient
DABCO 1,4-Diazabicyclo[2.2.2]octane
DCC Dynamic Covalent Chemistry
DCM Dichloromethane
DCTB trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene]malononitrile
DIBAL-H Di-iso-butylaluminium hydride
DMSO Dimethylsulfoxide
DOSY Diffusion-Ordered Spectroscopy
EA Elemental Analysis
EM Effective Molarity
G Gibbs Free Energy
H Enthalpy
ITC Isothermal Titration Calorimetry
K Association Constant
a
k Boltzmann Constant
B
K Intrinsic Binding Constant
i
K Statistical Factor
σ
MALDI Matrix-Assisted Laser Desorption/Ionization
MOF Metal Organic Framework
MOMCl Methoxymethyl chloride
MS Mass Spectrometry
N Avogadro constant
A
NBS N-Bromosuccinimide
v
NMR Nuclear Magnetic Resonance
OAc Acetoxy
OMIM Organic Monomer with Intrinsic Microporosity
ORTEP Oak Ridge Thermal Ellipsoid Plot
OTf Trifluoromethanesulfonate
PIM Polymer with Intrinsic Microporosity
PM6 Parameterization Method 6
ppm Parts Per Million
p-TsOH para-Toluenesulfonic acid
Q Heat Change
R Gas Constant
r Radius
R Retention factor
f
rt Room Temperature
S Entropy
TBAF Tetra-n-butylammonium fluoride
TBTQ Tribenzotriquinacene
TES Triethylsilyl
TFA Trifluoroacetic acid
THC Tetrahedral Character
THF Tetrahydrofuran
TLC Thin Layer Chromatography
TMS Trimethylsilyl
TOF Time of flight
tpt 2,4,6-Tri(4-pyridyl)-1,3,5-triazine
η Viscosity
ρ Density
σ Symmetry Number
σ External Symmetry Number
ext
σ Internal Symmetry Number
int

vi
Table of Contents

Chapter 1 - Aim of the Thesis ........................................................... 1

Chapter 2 - Literature Survey .......................................................... 5

2.1 Boron-Nitrogen Dative Bonds in Supramolecular Assemblies .................................... 5 
2.1.1 Geometry and Stability of Boron-Nitrogen Dative Bonds ..................................... 7 
2.1.2 Boron-Nitrogen Dative Bonds as Secondary Interactions .................................... 10 
2.1.3 Boron-Nitrogen Dative Bonds as Primary Interactions ........................................ 13 
2.2 Tribenzotriquinacene ................................................................................................... 19 
2.2.1 Structural Analysis ............................................................................................... 21 
2.2.2 Synthesis of the TBTQ Scaffold ........................................................................... 21 
2.2.3 Bridgehead-Functionalization .............................................................................. 23 
2.2.4 Outer rim-Functionalization ................................................................................. 27 
2.2.5 Ortho-Functionalization ....................................................................................... 30 
2.2.6 Apical-Functionalization ...................................................................................... 31 
2.3 Framework Materials .................................................................................................. 33 
2.3.1 Covalent Organic Cage Compounds .................................................................... 34 
2.3.2 Endohedral Functionalization of Covalent Organic Cage Compounds ............... 36 
2.3.3 Exohedral Functionalization of Covalent Organic Cage Compounds.................. 38 
Chapter 3 - Results and Discussion ................................................ 40

3.1 An Organic Cage Linked by Boron-Nitrogen Dative Bonds ...................................... 40 
3.1.1 Design Principle ................................................................................................... 40 
3.1.2 Model System ....................................................................................................... 42 
3.1.3 Supramolecular Cage Based on Boron-Nitrogen Dative Bonds .......................... 46 
3.1.4 Stimuli-Responsive Switching ............................................................................. 55 
3.2 Apical Functionalization of Tribenzotriquinacene ...................................................... 59 
3.2.1 Design Principles .................................................................................................. 60 
3.2.2 Synthesis of Apically Functionalized Tribenzotriquinacene ................................ 62 
3.2.3 Deprotection of Methoxy Groups ......................................................................... 67 
3.2.4 Apically Functionalized Tribenzotriquinacenes ................................................... 68 
vii
3.3 Functionalized Organic Cages .................................................................................... 72 
3.3.1 Exohedral Cage Functionalization ....................................................................... 72 
3.3.2 Synthesis of a 2-Substituted-meta-diboronic Acid .............................................. 76 
3.3.3 Towards the Formation of Cages Possessing Both Interior and Exterior
Functionalities ............................................................................................................... 82 
Chapter 4 - Summary ...................................................................... 86

Chapter 5 - Zusammenfassung ....................................................... 90

Chapter 6 - Experimental Section .................................................. 95

6.1 Materials and Methods ............................................................................................... 95 
6.2 Synthesis and Characterization ................................................................................... 96 
References ....................................................................................... 111

Appendix ......................................................................................... 120

Crystallographic Data ..................................................................................................... 120 
Analytical Data ............................................................................................................... 123 
Titration Data .................................................................................................................. 145 
1H-NMR Spectroscopy ............................................................................................... 145 
Isothermal Titration Calorimetry (ITC) ...................................................................... 147 
Acknowledgements ........................................................................ 149

viii