“Synthesis and structural characterization of NiII coordination polymers with neutral aromatic ligands with N-donors”

Postgraduate Thesis uoadl:2898521 243 Read counter

Unit:
Κατεύθυνση Ανόργανη Χημεία και Εφαρμογές της στη Βιομηχανία
Library of the School of Science
Deposit date:
2020-02-29
Year:
2020
Author:
Fontis Fani
Supervisors info:
Χριστίνα – Άννα Μητσοπούλου, Καθηγήτρια Ανόργανης Χημείας Εθνικού και
Καποδιστριακού Πανεπιστημίου Αθηνών
Original Title:
«Σύνθεση και δομική μελέτη πολυμερών συμπλόκων του NiΙΙ με ουδέτερους αρωματικούς υποκαταστάτες με Ν-δότες»
Languages:
Greek
Translated title:
“Synthesis and structural characterization of NiII coordination polymers with neutral aromatic ligands with N-donors”
Summary:
The scope of the present work is the synthesis and structural characterization of NiII coordination polymers with neutral aromatic ligands with N-donors, in particular the 1,2-bis(4-pyridyl)ethane (bpa) and the 1,2-bis(4-pyridyl)ethylene (bpe).
The effect of various factors on the nature of the products with respect to the dimensionality and topological diversity of the frameworks was examined, i.e. the reaction solvents, the reactants’ ratio, the crystallization method and temperature, the nature of the metal anions, and the nature of the ligands. Eleven coordination polymers were isolated, [Ni(bpa)2(H2O)2]n(OMe)2n.0.2nH2O (1), [Ni(bpa)2(H2O)2]n(OMe)2n.3.6nH2O (2), [Ni(bpa)2(H2O)2]n(OMe)2n (3), [Ni(bpa)2(H2O)2]n(OMe)2n.3.5nH2O (4), [Ni(bpa)2(H2O)2]n(OMe)2n (5), [Ni(bpa)2(H2O)2]n(ClO4)2n.2nMeOH (6), [Ni(bpa)1.5(NO3)2]n.0.5nMeOH (7), [Ni(bpe)3(H2O)2]n(ClO4)2n•nbpe•nH2O (8), [Ni(O2CPh)2(H2O)(bpa)1.5]n (9), [Ni(bpe)2(H2O)2]n(NO3)2n.2nMeOH.0.7nH2O (10), και [Ni(O2CPh)2(H2O)(bpe)1.5]n.nMe2CO (11). Coordination polymers 1-7, 10 were synthesized and studied for the first time during this work, while coordination polymers 8, 9, and 11 were known in the literature and their synthesis was repeated for further study of their physical properties.
The coordination polymers 1-5 consist of the [Ni(bpa)2(H2O)2]2+ cation, MeO- anions, and H2O lattice solvents. The coordination environment of the NiII ion consists of four nitrogen atoms from four bpa ligands and two oxygen atoms from the two aqua ligands. Each bpa ligand is coordinated through the pyridine nitrogen atoms to two NiII ions and bridges two metal ions by adopting the anti-configuration (Cpy-C-C-Cpy ~ 180°) resulting in the formation of two-dimensional frameworks described as 2D (4.4). The methoxy anions and the solvents lie outside the two-dimensional framework and participate in hydrogen bonds. The two-dimensional layers interpenetrate and form a three-dimensional framework described as interpenetrating 2D(4,4). The 2D frameworks in 2 and 4 show a wave-structure in contrast to the planar framework structure in 1. This results in different pore shape between polymers 1 and 2, 4. The pores in 1, 2 and 4 occupy the ~ 45% of the total cell unit volume and are filled by the methoxy anions and the solvents.
The coordination polymer 6 consists of the [Ni(bpa)2(H2O)2]2+cation, ClO4- anions, and MeOH lattice solvents. The coordination environment of the NiII ion consists of four nitrogen atoms from four bpa ligands and two oxygen atoms from the two aqua ligands. Each bpa ligand is coordinated through the pyridine nitrogen atoms to two NiII ions and bridges two metal ions by adopting the gauche-configuration (Cpy-C-C-Cpy ~ 66 °) resulting in the formation of one-dimensional structure. The perchlorate anions and the lattice solvents lie out of the one-dimensional structure and participate in hydrogen bonds resulting in the formation of a supramolecular two-dimensional lattice.
The coordination polymer 7 consists of the [Ni(bpa)1.5(NO3)2] complex and MeOH solvents. The coordination environment around the NiII ion is octahedral and consists of three nitrogen atoms derived from three bpa ligands and three oxygen atoms from two nitrates which adopt the bidentate chelate and the monodentate coordination modes. Each bpa ligand coordinates through the pyridine nitrogen atoms to two NiII ions acting as bridges. The two bpa ligands adopt the anti-configuration (Cpy-C-C-Cpy ~ 180°) and bridge two NiII ions leading to two-dimensional framework. The third bpa ligand adopts the gauche-configuration (Cpy-C-C-Cpy ~ 55°).
The coordination polymer 10 consists of the [Ni(bpe)2(H2O)2]2+ cation, NO3- anions, and MeOH/H2O lattice solvents. The coordination environment around the NiII ion is octahedral and consists of four nitrogen atoms from four bpe ligands and two oxygen atoms of two aqua ligands. Each bpe ligand is coordinated through the pyridine nitrogen atoms to two NiII ions and acts as bridging by adopting the anti-configuration (Cpy-C-C-Cpy ~ 180 °) thus resulting in the formation of two-dimensional frameworks 2D(4.4). Nitrate anions and solvents lie out of the 2D lattice and participate in hydrogen bonds. The two-dimensional lattices interpenetrate and form a three-dimensional framework described as interpenetrating 2D(4,4). The pores occupy ~44% of the total unit cell volume.
Main subject category:
Science
Keywords:
Coordination polymers, Nickel, Aromatic ligands, Synthesis, Crystallography
Index:
No
Number of index pages:
0
Contains images:
No
Number of references:
154
Number of pages:
155
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