{"id":{"repo_id":"unsw","oai_identifier":"oai:unsworks.library.unsw.edu.au:1959.4/54515"},"canonical_url":"https://search.dev.ndltd.org/etd/unsw/oai:unsworks.library.unsw.edu.au:1959.4/54515","repository":{"repo_id":"unsw","name":"University of New South Wales","base_url":"https://unsworks.unsw.edu.au/oai/provider"},"display":{"title":"Luminescent Iridium(III) Cyclometalated Complexes: Host-Guest Chemistry and Application as Sensors","abstract":"In this thesis, known and new iridium(III) cyclometalated complexes have been synthesized and investigated in a host-guest chemical context and in studies towards an application in the detection of peroxide-based explosives in fingerprints. The complexes [Ir(ppy-R)2(bpy)]n+ studied here contain two cyclometalated ligands (ppy-R: R-substituted 2-phenylpyridine), and one polypyridine ligand (bpy=2,2 -bipyridine). Substituent groups R included: R=H (Ir-H); R=CHO (Ir-CHO); R=CH2NH-Bu, Bu=n-butylamine, (Ir-CH2NH-Bu); R=CH2NH-Oct, Oct=n-octylamine (Ir-CH2NH-Oct); and R=CH2N-(Oct)2 (Ir-CH2N-(Oct)2). Chapter 2 demonstrated that the R group in the iridium(III) complexes significantly affects the photophysical properties. Luminescence and electrochemical studies confirmed that the CHO group acts as a strong electron withdrawing group (EWG), while Ir-CH2NH-Bu was more like Ir-H, as the n-butyl group (Bu) behaved as a mild EWG rather than an electron donating group (EDG). Ir-CHO and Ir-H both showed similar responses to solvent polarity, but the response of Ir-CH2NH-Bu was opposite to that observed for Ir-CHO and Ir-H. In the iridium alkylamine complexes, Ir-CH2N-(Oct)2 displayed different emission properties from Ir-CH2NH-Bu and Ir-CH2NH-Oct. In the host-guest study reported in Chapter 3, all complexes (Ir-CHO, Ir-H and Ir-CH2NH2+-Bu) showed a similar accommodation mode within Q[10], where the ppy-R ligands sat deep within the cavity while the bpy ligand sat on the portal. In the presence of Q[10] the emission profiles of these complexes showed enhanced intensity with blue shifts and became more structured. The titration study showed that both Ir-CHO and Ir-H had similar binding behavior (1:2 portal bound and 1:1 cavity bound) while Ir-CH2NH2+-Bu only displayed 1:1 cavity bound associations. The emissions of encapsulated complexes were found to be very sensitive to temperature. In Chapter 4 this type of Ir(III) cyclometalated complex was applied toward a detection application for both fingerprints and peroxide-based explosives in the oil of fingerprints. Ir-CH2N-(Oct)2 displayed the highest solubility in oleic acid (as an example of fatty acid that present in fingerprints). A boronic acid group (B(OH)2) was introduced to the bpy ligand to form B(OH)2-Ir-H, which was used as a sensor for peroxide detection, based on the ability of hydrogen peroxide (H2O2) to oxidize a boronic acid group and hence induce a change in the luminescence.","abstract_html":"In this thesis, known and new iridium(III) cyclometalated complexes have been synthesized and investigated in a host-guest chemical context and in studies towards an application in the detection of peroxide-based explosives in fingerprints. The complexes [Ir(ppy-R)2(bpy)]n+ studied here contain two cyclometalated ligands (ppy-R: R-substituted 2-phenylpyridine), and one polypyridine ligand (bpy=2,2 -bipyridine). Substituent groups R included: R=H (Ir-H); R=CHO (Ir-CHO); R=CH2NH-Bu, Bu=n-butylamine, (Ir-CH2NH-Bu); R=CH2NH-Oct, Oct=n-octylamine (Ir-CH2NH-Oct); and R=CH2N-(Oct)2 (Ir-CH2N-(Oct)2). Chapter 2 demonstrated that the R group in the iridium(III) complexes significantly affects the photophysical properties. Luminescence and electrochemical studies confirmed that the CHO group acts as a strong electron withdrawing group (EWG), while Ir-CH2NH-Bu was more like Ir-H, as the n-butyl group (Bu) behaved as a mild EWG rather than an electron donating group (EDG). Ir-CHO and Ir-H both showed similar responses to solvent polarity, but the response of Ir-CH2NH-Bu was opposite to that observed for Ir-CHO and Ir-H. In the iridium alkylamine complexes, Ir-CH2N-(Oct)2 displayed different emission properties from Ir-CH2NH-Bu and Ir-CH2NH-Oct. In the host-guest study reported in Chapter 3, all complexes (Ir-CHO, Ir-H and Ir-CH2NH2+-Bu) showed a similar accommodation mode within Q[10], where the ppy-R ligands sat deep within the cavity while the bpy ligand sat on the portal. In the presence of Q[10] the emission profiles of these complexes showed enhanced intensity with blue shifts and became more structured. The titration study showed that both Ir-CHO and Ir-H had similar binding behavior (1:2 portal bound and 1:1 cavity bound) while Ir-CH2NH2+-Bu only displayed 1:1 cavity bound associations. The emissions of encapsulated complexes were found to be very sensitive to temperature. In Chapter 4 this type of Ir(III) cyclometalated complex was applied toward a detection application for both fingerprints and peroxide-based explosives in the oil of fingerprints. Ir-CH2N-(Oct)2 displayed the highest solubility in oleic acid (as an example of fatty acid that present in fingerprints). A boronic acid group (B(OH)2) was introduced to the bpy ligand to form B(OH)2-Ir-H, which was used as a sensor for peroxide detection, based on the ability of hydrogen peroxide (H2O2) to oxidize a boronic acid group and hence induce a change in the luminescence.","abstract_has_math":false,"creators":["Alrawashdeh, Lubna"],"institution":"UNSW, Sydney","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015","date_published":"2015","updated_at":"2026-07-24T05:33:55Z","subjects":["photophysical properties","Iridium(III) cyclometalated complexes","Cucurbituril"],"languages":["EN"],"rights":["open access","CC BY-NC-ND 3.0","free_to_read"],"rights_urls":["https://purl.org/coar/access_right/c_abf2","https://creativecommons.org/licenses/by-nc-nd/3.0/au/"],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.26190/unsworks/2768"],"render_values":[{"text":"https://doi.org/10.26190/unsworks/2768","href":"https://doi.org/10.26190/unsworks/2768","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/1959.4/54515","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Alrawashdeh, Lubna"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015"]},{"key":"dc:publisher","label":"Institution","values":["UNSW, Sydney"]},{"key":"dc:type","label":"Dc Type","values":["doctoral thesis","http://purl.org/coar/resource_type/c_db06"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["photophysical properties","Iridium(III) cyclometalated complexes","Cucurbituril"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["EN"]},{"key":"dc:rights","label":"Dc Rights","values":["open access","https://purl.org/coar/access_right/c_abf2","CC BY-NC-ND 3.0","https://creativecommons.org/licenses/by-nc-nd/3.0/au/","free_to_read"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/1959.4/54515","https://unsworks.unsw.edu.au/bitstreams/4d8f1e21-e551-4664-86dc-ffad56792826/download","https://doi.org/10.26190/unsworks/2768"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In this thesis, known and new iridium(III) cyclometalated complexes have been synthesized and investigated in a host-guest chemical context and in studies towards an application in the detection of peroxide-based explosives in fingerprints. The complexes [Ir(ppy-R)2(bpy)]n+ studied here contain two cyclometalated ligands (ppy-R: R-substituted 2-phenylpyridine), and one polypyridine ligand (bpy=2,2 -bipyridine). Substituent groups R included: R=H (Ir-H); R=CHO (Ir-CHO); R=CH2NH-Bu, Bu=n-butylamine, (Ir-CH2NH-Bu); R=CH2NH-Oct, Oct=n-octylamine (Ir-CH2NH-Oct); and R=CH2N-(Oct)2 (Ir-CH2N-(Oct)2). Chapter 2 demonstrated that the R group in the iridium(III) complexes significantly affects the photophysical properties. Luminescence and electrochemical studies confirmed that the CHO group acts as a strong electron withdrawing group (EWG), while Ir-CH2NH-Bu was more like Ir-H, as the n-butyl group (Bu) behaved as a mild EWG rather than an electron donating group (EDG). Ir-CHO and Ir-H both showed similar responses to solvent polarity, but the response of Ir-CH2NH-Bu was opposite to that observed for Ir-CHO and Ir-H. In the iridium alkylamine complexes, Ir-CH2N-(Oct)2 displayed different emission properties from Ir-CH2NH-Bu and Ir-CH2NH-Oct. In the host-guest study reported in Chapter 3, all complexes (Ir-CHO, Ir-H and Ir-CH2NH2+-Bu) showed a similar accommodation mode within Q[10], where the ppy-R ligands sat deep within the cavity while the bpy ligand sat on the portal. In the presence of Q[10] the emission profiles of these complexes showed enhanced intensity with blue shifts and became more structured. The titration study showed that both Ir-CHO and Ir-H had similar binding behavior (1:2 portal bound and 1:1 cavity bound) while Ir-CH2NH2+-Bu only displayed 1:1 cavity bound associations. The emissions of encapsulated complexes were found to be very sensitive to temperature. In Chapter 4 this type of Ir(III) cyclometalated complex was applied toward a detection application for both fingerprints and peroxide-based explosives in the oil of fingerprints. Ir-CH2N-(Oct)2 displayed the highest solubility in oleic acid (as an example of fatty acid that present in fingerprints). A boronic acid group (B(OH)2) was introduced to the bpy ligand to form B(OH)2-Ir-H, which was used as a sensor for peroxide detection, based on the ability of hydrogen peroxide (H2O2) to oxidize a boronic acid group and hence induce a change in the luminescence."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Luminescent Iridium(III) Cyclometalated Complexes: Host-Guest Chemistry and Application as Sensors"]}]}],"canonical_facts":{"dc:creator":["Alrawashdeh, Lubna"],"dc:date":["2015"],"dc:description":["In this thesis, known and new iridium(III) cyclometalated complexes have been synthesized and investigated in a host-guest chemical context and in studies towards an application in the detection of peroxide-based explosives in fingerprints. The complexes [Ir(ppy-R)2(bpy)]n+ studied here contain two cyclometalated ligands (ppy-R: R-substituted 2-phenylpyridine), and one polypyridine ligand (bpy=2,2 -bipyridine). Substituent groups R included: R=H (Ir-H); R=CHO (Ir-CHO); R=CH2NH-Bu, Bu=n-butylamine, (Ir-CH2NH-Bu); R=CH2NH-Oct, Oct=n-octylamine (Ir-CH2NH-Oct); and R=CH2N-(Oct)2 (Ir-CH2N-(Oct)2). Chapter 2 demonstrated that the R group in the iridium(III) complexes significantly affects the photophysical properties. Luminescence and electrochemical studies confirmed that the CHO group acts as a strong electron withdrawing group (EWG), while Ir-CH2NH-Bu was more like Ir-H, as the n-butyl group (Bu) behaved as a mild EWG rather than an electron donating group (EDG). Ir-CHO and Ir-H both showed similar responses to solvent polarity, but the response of Ir-CH2NH-Bu was opposite to that observed for Ir-CHO and Ir-H. In the iridium alkylamine complexes, Ir-CH2N-(Oct)2 displayed different emission properties from Ir-CH2NH-Bu and Ir-CH2NH-Oct. In the host-guest study reported in Chapter 3, all complexes (Ir-CHO, Ir-H and Ir-CH2NH2+-Bu) showed a similar accommodation mode within Q[10], where the ppy-R ligands sat deep within the cavity while the bpy ligand sat on the portal. In the presence of Q[10] the emission profiles of these complexes showed enhanced intensity with blue shifts and became more structured. The titration study showed that both Ir-CHO and Ir-H had similar binding behavior (1:2 portal bound and 1:1 cavity bound) while Ir-CH2NH2+-Bu only displayed 1:1 cavity bound associations. The emissions of encapsulated complexes were found to be very sensitive to temperature. In Chapter 4 this type of Ir(III) cyclometalated complex was applied toward a detection application for both fingerprints and peroxide-based explosives in the oil of fingerprints. Ir-CH2N-(Oct)2 displayed the highest solubility in oleic acid (as an example of fatty acid that present in fingerprints). A boronic acid group (B(OH)2) was introduced to the bpy ligand to form B(OH)2-Ir-H, which was used as a sensor for peroxide detection, based on the ability of hydrogen peroxide (H2O2) to oxidize a boronic acid group and hence induce a change in the luminescence."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/1959.4/54515","https://unsworks.unsw.edu.au/bitstreams/4d8f1e21-e551-4664-86dc-ffad56792826/download","https://doi.org/10.26190/unsworks/2768"],"dc:language":["EN"],"dc:publisher":["UNSW, Sydney"],"dc:rights":["open access","https://purl.org/coar/access_right/c_abf2","CC BY-NC-ND 3.0","https://creativecommons.org/licenses/by-nc-nd/3.0/au/","free_to_read"],"dc:subject":["photophysical properties","Iridium(III) cyclometalated complexes","Cucurbituril"],"dc:title":["Luminescent Iridium(III) Cyclometalated Complexes: Host-Guest Chemistry and Application as Sensors"],"dc:type":["doctoral thesis","http://purl.org/coar/resource_type/c_db06"]},"updated_at":"2026-07-24T05:33:55Z"}