Khaled Hassanein Sayed Ahmed

261 Pages·2016·13.56 MB·English

One Dimensional Coordination Polymers with Molecular
Recognition Capability as Dynamic and Multifunctional
Materials.

By
Khaled Hassanein Sayed Ahmed

Supervised by
Dr. Pilar Amo Ochoa Dr. Félix Zamora Abanades

This dissertation has been submitted to
Departamento de Química Inorgánica
Facultad de Ciencias
Universidad Autónoma de Madrid
in fulfillment of the degree of Doctorate in Chemistry

Madrid, 2016

Acknowledgements
It is difficult to decide whom to thank first, but I think it has to start with my big family,
my parents and my sisters (Iman, Asmaa, and Donia). The support you have given me
over the years with regard to my education has been invaluable. In particular, especial
thank for my mother for being the only supporter in the difficult moments and for taking
my responsibility as the host of my family during the last years, thank you my mother.
My lovely wife (Hind), and my little son (Abdelrahman), you are the key of happiness
for me in this world.
On the other hand, it was impossible to finish this thesis without the support of my
advisors, Dr. Pilar Amo Ochoa and Dr. Félix Zamora Abanades. Thank you Dr. Pilar
Amo for countless hours you have spent to help me through every step of my dissertation.
Your advices and encouragements have been unending and invaluable, guiding me to
define the direction of my research. Thank you Dr. Félix Zamora, your attentions for the
details have helped me to hone my ideas and improve the quality of my dissertation.
Especial thanks for the investigators who have collaborated with us to finish this thesis.
Thanks for Dr. Óscar Castillo, from Universidad del País Vasco, and Dr. Josefina
Perles, from Servicio Interdepartamental de Investigación (SIDI) at Univesidad
Autónoma de Madrid, for their contributions in the single crystal X-ray diffraction
measurements, structural refinements, and structural descriptions. Thanks for Dr. Carlos
Gómez, from Instituto de Ciencia Molecular (ICMOL), and Dr. Pilar Ocon, from
Univesidad Autónoma de Madrid, for the conductivity measurements. Thanks for Prof.
Dr. Salomé Delgado, Dr. Marcos Zayat, and Virginia Vadillo, from Univesidad
Autónoma de Madrid, for photoluminescence measurements. Thanks for Dr. José
Ignacio Martínez, from Instituto de Ciencia de Materiales, CSIC, for the DFT
calculations. Thanks for Dr. Álvaro Somoza, Romina Lorca, and Ana Latorre, from
Instituto IMDEA Nanociencia, for biological studies.
I want to thank my colleagues who participated in the experimental part of this thesis.
Thank you Javier Conesa, Fatima, and Veronica.
I want to thank the present and old members of the Nanomaterials group, Cristina
Hermosa, Isadora Berlanga, Mohamed Reza, Azin Hassanpour, David Rodríguez, Jesus,
Pablo, Carlos, Alex, and Carmen. Thank you for my close friend Javier Troyano for being

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available a lot of hours for discussions, sharing your opinions, and removing stress in
hard moments.
Thank you for the workers of the Inorganic department for being always available and
ready for problem solving. Thank you Miguel Angel, Ismael, and Nani.
Thank you for my Egyptian friends in Spain, with you I feel as if I am in my home
country. Thank you Mohamed Moaid, Walid, Safawat, Moahmed abdel Kader, Edris,
Fouad, Dr Tag, Hassan, Hitham, Imad, and Yousef.
I want to admire and address my thanks for all the professors who teach me in all my life
stages especial those who forming my knowledge in chemistry.
Also, I would like to thank my dear friends living in Egypt. Mohamed Abdel Fatah,
Osama, Hany, Sabry, Tamer, Mohamed Ismaeil, Khalaf, Mr. Adel Mahmoud, Hala,
Nahla, and all the members of my family.
Finally, I have to mention that this work was funded by Spanish Ministry of Science and
Innovation (MICINN) through grant MAT2010-20843-C02-01.

Thank you for all.

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Publications and Conferences

Publications included in this thesis
 Semiconductive and Magnetic One-Dimensional Coordination Polymers of Cu(II) with
Modified Nucleobases.
Pilar Amo-Ochoa, Oscar Castillo, Carlos J. Gómez-García, Khaled Hassanein, Sandeep
Verma, Jitendra Kumar and Félix Zamora. Inorg. Chem, 2013, 52 (19), pp 11428–11437.
dx.doi.org/10.1021/ic401758w.
 Asymmetric and symmetric dicopper(II) paddle-wheel units with modified nucleobases.
Khaled. Hassanein, Pilar Amo-Ochoa, Oscar Castillo, Carlos J. Gómez-García and Félix
Zamora. Cryst. Growth Des, 2015, 15 (11), pp 5485–5494. DOI: 10.1021/acs.cgd.5b01110.
 Reversible stimulus-responsive Cu(I) iodide pyridine coordination polymer.
Pilar Amo-Ochoa, Khaled Hassanein, Carlos J. Gómez-García, Samira Benmansour,
Josefina Perles, Oscar Castillo, José I. Martínez, and Félix Zamora. Chem. Commun, 2015,
51, pp 14306-14309. DOI: 10.1039/C5CC04746C.
 Electrical Conductivity and Strong Luminescence in Copper-Iodide Double-Chains with
Isonicotinato Derivatives.
Khaled Hassanein, Javier Conesa-Egea, Salome Delgado, Oscar Castillo, Samia
Benmansour, José I. Martínez, Gonzalo Abellán, Carlos J. Gómez-García, Félix Zamora
and Pilar Amo-Ochoa. Chem. Eur. J, 2015, 21, pp 1 – 12. DOI: 10.1002/chem.201502131.
 Halo- and pseudohalo Cu(I)-pyridinato double chains with tunable physical properties.
Khaled Hassanein, Pilar Amo-Ochoa, Carlos J. Gómez-García, Salomé Delgado, Oscar
Castillo and Félix Zamora. Inorg. Chem, 2015, 54 (22), pp 10738–10747. DOI:
10.1021/acs.inorgchem.5b01754.

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Accepted publications included in this thesis
 Co(II)-modified nucleobases complexes. A methyl care?
Khaled Hassanein, Félix. Zamora, Oscar Castillo and Pilar Amo-Ochoa. Inorganica
chimica acta, 2016.

Publications in progress included in this thesis
 Biocompatible Molecular Thick Nanoribbons of a Multifuntional 1D-Cu(II)-
nucleobase coordination polymer showing Molecular Recognition towards
Oligonucleotides.
Khaled Hassanein, Verónica García, Romina Lorca, Ana Latorre, Álvaro Somoza, P.
Amo-Ochoa, Carlos J. Gómez-García, Oscar Castillo, and F. Zamora. In preparation.

Conferences
 40 International Conference on Coordination Chemistry” (ICCC40), Valencia, Spain,
Sep. 9-13, 2012.
 The 15th Asian Chemical Congress, Singapore, Aug. 19-23, 2013.
 XXIV Symposium of the Specialized Group on Crystallography and Crystal Growth
(GE3C) at Bilbao, Spain, 2014.
 5th Molecular Materials Meeting (M3) @ Singapore An international conference on the ”Next
50 Years In Materials Research” Aug. 19-23, 2015.
 First National Symposium on properties and applications of MOFs and COFs at
Granada, Spain, 2015.

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List of abbreviations
0D-CPs Zero dimensional coordination polymers
1D-CPs One dimensional coordination polymers
1D-NCPs Nanoscale one dimensional coordination polymers
2D-CPs Two dimensional coordination polymers
3D-CPs Three dimensional coordination polymers
4,4'-bipy 4,4'-Bipyridine
6-MP 6-Mercaptopurine
6-TG 6-Thioguanine
AC current
AFM Atomic force microscopy
ANP 2-Amino-5-nitropyridine
Bio-NCPs Nanoscale coordination polymers containing biomolecules as ligands
CAFM Conductance atomic force microscopy
CITS Current imaging tunneling spectroscopy
COFs Covalent organic frameworks
CPs Coordination polymers
DC Direct current
DFT Density function theory
DMA Dimethylacetamide
DMF Dimethylformamide
DMSO Dimethyl sulfoxide
DNA Deoxyribonucleic acid
E Activation energy
a
E Energy gab
g
EIS Electrochemical impedance spectroscopy
Et O Diethyl ether
2
EtIN Ethyl isonicotinate
FESEM Field emission scanning electron microscope

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H Applied magnetic field
H Coercivity or coercive field
C
HDap 2,6-Diaminopurine
HE High-energy band
HIN Isonicotinic acid
HOPG Highly ordered pyrolytic graphite
HS High spin
HOMO Highest occupied molecular orbital
IC Internal conversion
IR Infrared spectroscopy
ISC Intersystem crossing
J Magnetic exchange coupling constant
L Liter
LC Ligand-centered
LE Low-energy band
LMCT Ligand-to-metal charge transfer
LS Low spin
LUMO Lowest unoccupied molecular orbital
M Magnetization
MC Metal-center
MeCN Acetonitrile
MeOH Methanol
MLCT Metal-to-ligand charge transfer
MOCNs Metal-organic coordination networks
MOFs Metal-organic frameworks
NBs Nucleobases
PCPs Porous coordination polymers
PL Photoluminescence
SBU Secondary building unit

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SCO Spin-crossover
SCSC Single-crystal to single-crystal
SCXRD Single crystal X-ray diffraction
SQUID Superconducting quantum interference device technique
STM Scanning tunneling microscope
STS Scanning tunneling spectroscopy
TAcOH Thymine-1-acetic acid
TCNQ 5,7,7,8,8-tetracyanoquinodimethane
TGA Thermogravimetric analysis
Trans-bie Trans-bis(N-methylimidazol-2-yl)ethylene
UAcOH Uracil-1-acetic acid
UV-Vis Ultraviolet-visible spectrophotometry
XLCT Halide-to-ligand charge transfer
XRPD X-ray Powder diffraction
 Angle
 Conductivity
 Wavelength
 Resistivity
  Molar magnetic susceptibility
m
Ă Angstroms
g Gram

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