Computational Chemistry of Supramolecular Systems - Ab Initio and DFT Studies

212 Pages·2012·11.52 MB·English

Computational Chemistry of
Supramolecular Systems
-
Ab Initio and DFT Studies
Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der RWTH Aachen University zur Erlangung des akademischen Grades
einer Doktorin der Naturwissenschaften genehmigte Dissertation
vorgelegt von
Diplom-Chemikerin
Verena Moha, geb. Gossen
aus Stolberg (Rhld.)
Berichter: Univ.-Professor Dr. rer. nat. M. Albrecht
apl. Professor Dr. rer. nat. G. Raabe
Tag der mündlichen Prüfung: 03.08.2012
Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.
To my parents
It doesn’t matter how beautiful your theory is,
it doesn’t matter how smart you are.
If it doesn’t agree with experiment, it’s wrong.
Richard Feynman

The computational studies of this thesis have been performed from september 2009
until January 2012 at the Institute of Organic Chemistry at the RWTH Aachen uni-
versity under the supervision of Prof. Dr. Markus Albrecht and Prof. Dr. Gerhard
Raabe.
Parts of the described results have already been published:
1. "Anion-π Interactions in Salts with Polyhalide Anions: Trapping of I2−" - M.
4
Müller, M. Albrecht, V. Gossen, T. Peters, A. Hoffmann, G. Raabe, A. Valkonen,
K. Rissanen, Chem. Eur. J. 2010, 16, 12446.
2. "Induced Fit in Chiral Recognition: Epimerization upon Dimerization in the
Hierarchical Self-Assembly of Helicate-type Titanium(IV) Complexes"- M. Al-
brecht, E. Isaak, M. Baumert, V. Gossen, G. Raabe, R. Fröhlich, Angew. Chem.
Int. Ed. 2011, 50, 2850.
3. "Cooperativity of H-bonding and anion- interaction in the binding of anions with
neutral -acceptors" - M. Giese, M. Albrecht, T. Krappitz, M. Peters, V. Gossen,
G.Raabe,A.Valkonen,K.Rissanen: Chem. Comm.,DOI:10.1039/C2CC34748B.
Parts of the described results were part of bachelor thesis:
1. S. Mommer, Bachelor thesis 2010, RWTH Aachen (chapter 5.1)
2. R.Kozik, Bachelor thesis 2010, RWTH Aachen (chapter 5.1)
My greatful thanks go to Prof. Dr. Markus Albrecht for the interesting topic, his
continuous interest in the process of this work, and for the left liberties.
My grateful thanks go to Prof. Dr. Gerhard Raabe for his continous interest in
the process of this work, his support with questions regarding the field of theoretical
chemistry, and for being my co-advisor.

Contents
1 Introduction 1
1.1 Supramolecular Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Project Aim . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3 Computational Details . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4 CD Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2 Anion - π Interactions 16
2.1 Studies of Interactions with Anions . . . . . . . . . . . . . . . . . . . . 16
2.2 Studies of Interactions with Dianions . . . . . . . . . . . . . . . . . . . 20
3 Mononuclear Complexes 26
3.1 Mononuclear Complexes with Pincer Ligands . . . . . . . . . . . . . . . 26
3.2 Mononuclear Complexes with Triscatecholate-Based Ligands . . . . . . 45
3.3 Dimerization of Triscatecholate-Based Complexes . . . . . . . . . . . . 51
3.4 TD-DFT studies of Triscatecholate-Based Complexes . . . . . . . . . . 56
4 Binuclear Complexes 129
4.1 Homodinuclear Complexes with Alkyl-Bridged Dicatecholate-Ligands . 129
4.2 Homodinuclear Complexes with Imino-Bridged Ligands . . . . . . . . . 139
4.3 Heterodinuclear Complexes with Bishydroxychinoline-Based Ligands . . 145
4.4 Heterodinuclear Complexes with Dicatecholate-Based Ligands . . . . . 153
5 Tetranuclear Complexes 164
5.1 Tetranuclear Helicates . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.2 Molecular Tetrahedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6 Summary 194
A References 197
i
ii
Acronyms and Abbreviations
AO atomic orbital
a.u. atomic energy units (Hartrees)
B3LYP Becke Three Parameter Hybrid
c velocity of light
cam coulomb-attenuating method
cat catecholate
CD circular dichroism
DF density functional
DFT density functional theory
DMSO dimethyl sulfoxide
ECP electron core potential
fac facial
GGA generalized gradient approximation
h Planck’s constant
HEG homogeneous electron gas
HF Hartree Fock
HOMO highest occupied molecular orbital
KS Kohn Sham
λ wavelength
LDA local density approximation
LP lone pair
LUMO lowest unoccupied molecular orbital
MDF Dirac-Fock relativistic
MeOH methanol
iii
mer meridional
MMFF Merck Molecular force field
MO molecular orbital
MP2 Møller-Plesset perturbation to the second order
MWB molecular weight basis
N Avogadro’s number
A
NBO natural bond orbital
occ occupied
Ψ spin orbital
R rotational strength
RY Rydberg
SDD Stuttgart Dresden potential
TD time dependent
THF tetrahydrofuran
TZVP triple-zeta valence polarization
virt virtual
iv