Multivalent N-donor ligands for the construction of coordination polymers and coordination polymer gels
This work describes the synthesis and characterisation of several multivalent N-donor ligands and their coordination compounds and the use of these ligands in the construction of coordination polymers and coordination polymer gels. The project can be divided into two parts. The first part of the research is focused on the coordination chemistry of ring-substituted biimidazoles in acidic media. The dependence of the formation of ion pairs and zwitterionic, especially zinc and copper containing coordination compounds on the pH of the reaction medium and ring-substituents of the ligand were examined. The second part of the study deals with the preparation of Ag, Zn and Cu coordination polymers (CPs) and coordination polymer gels (CPGs) from geometrically flexible biimidazole- and bipyridine-based ligands. The effect of metal centres and reaction conditions on structural topologies of CPs was studied and presented in publication II. Since the CPGs were obtained by silver coordination, a new photochemical process was developed to form silver nanoparticles (AgNP) on the surface of the coordination polymeric fibers. The method was disclosed in publications III and IV. In order to explain and combine these different studies into one thesis, the following procedure was followed: first, an introduction to the N-donor ligands, especially biimidazole and bipyridines and their coordination chemistry in acidic and basic media was presented. The later part was focused on general synthetic routes for CPs and possibilities to control their structure with literature examples. The chapter then gives an introduction to the gels, and supramolecular metallogels with examples of recent publications and gel characterisation methods. The introduction ends with the aim of the study. The second part of the thesis outlines the most significant findings reported in the four original publications. The discussion part begins with a short chapter on the synthesis of a series of N-donor ligands, followed by their coordination chemistry in an acidic medium. The follow-up chapter deals with the construction of CPs and CPGs with semirigid ligands. The final chapter of the discussion ends with the luminescence properties of these CPs and CPGs. At the end of the thesis, these results are briefly summarised with significant findings. ...
PublisherUniversity of Jyväskylä
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Turunen, Lotta (University of Jyväskylä, 2017)This thesis describes the design, synthesis and characterization of supramolecular halogen-bonded capsules and cages from multivalent ligands. In the first part of the thesis, an overview to halogen bonding is provided. ...
In-depth structural analysis of lanthanoid coordination networks based on a flexible tripodal zwitterionic isonicotinate ligand Tiihonen, Antti; Lahtinen, Manu (Royal Society of Chemistry, 2019)Crystallizing metal–organic frameworks (MOFs) has been studied using a tripodal pyridinecarboxylic acid derivative ligand and selected lanthanoid salts. The zwitterionic ligand, 1,1′,1′′-((2,4,6-trimethylbenzene-1,3,5-tr ...
Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs Volbach, Lucia; Struch, Niklas; Bohle, Fabian; Topic, Filip; Schnakenburg, Gregor; Schneider, Andreas; Rissanen, Kari; Grimme, Stefan; Lützen, Arne (Wiley-VCH Verlag, 2020)Two isostructural ligands with either nitrile ( L nit ) or isonitrile ( L iso ) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself ...
Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes Pratt, Jade; Bryan, Aimee M.; Faust, Michelle; Boynton, Jessica N.; Vasko, Petra; Rekken, Brian D.; Mansikkamäki, Akseli; Fettinger, James C.; Tuononen, Heikki; Power, Philip P. (American Chemical Society, 2018)On the basis of work with earlier linear two-coordinate metal complexes of the amido [−NAriPr4 and −NAriPr6; AriPr4 = C6H3-2,6(C6H3-2,6-iPr2); AriPr6 = C6H3-2,6(C6H2-2,4,6-iPr3] or aryloxo (−OAriPr4 and −OAriPr6) ligands, ...
Kuosmanen, Riikka T.; Truong, Khai‐Nghi; Rissanen, Kari T.; Sievänen, Elina I. (Wiley-VCH Verlag, 2021)Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all ...