{"id":{"repo_id":"whiterose","oai_identifier":"oai:etheses.whiterose.ac.uk:1623"},"canonical_url":"https://search.dev.ndltd.org/etd/whiterose/oai:etheses.whiterose.ac.uk:1623","repository":{"repo_id":"whiterose","name":"White Rose University Consortium","base_url":"https://etheses.whiterose.ac.uk/cgi/oai2"},"display":{"title":"Crystal Structures of Helical Columnar pi-Conjugated Systems and Biodegradable Polyester","abstract":"Crystal structures of helical columnar pi-conjugated systems, namely helicene-bisquinone and dendronized perylene bisimide derivative as well as of a biodegradable aliphatic polyester, namely poly-9-hydroxynonanoate, have been resolved by means of fibre X-ray diffraction. Enantiopure and racemic helicene-bisquinones are found to be organized into columnar liquid crystalline phases. The internal structure of the columns is 132 hollow helix with the asymmetric unit comprised of six-molecules, hence of 78 molecules and two turns in a period of 112 Å. The long-range order among the columns is found to be laterally high but longitudinally - low. This is the first atomic-level determination of a helical columnar liquid crystalline phase. The crystal structure of N,N’-di-(3,4,5-dodecyloxy-oxyphenylethyl)-perylene bisimide is approximated by distorted helical columns arranged within an orthorhombic unit cell with lattice parameters a = 70.2 ± 0.02 Å, b = 41.1 ± 0.02 Å, and c = 45.5 ± 0.02 Å. The space group is determined to be P212121. The internal structure of the columns is approximated by 61 helices. The structure is based on four-molecule repeat units (tetramers). There are 24 molecules and two turns in a 45.51 Å period of the distorted 6-fold helix. The tetramer is comprised of 2 dimers (two boat-shaped molecules placed side-by-side) facing each other in the tetramer. The rotation angle between the dimers within the tetramer is 100°. Charge mobility along the columns has been found to depend critically on the detailed molecular packing. The crystal structure of poly-9-hydroxynonanoate is established to be polyethylene-like except that the ester groups are randomly distributed throughout the lattice. The molecular chain of poly-9-hydroxynonanoate is determined to possess planar zigzag conformation with two such chains arranged within an orthorhombic unit cell with lattice parameters, a = 7.47 ± 0.02 Å, b = 5.00 ± 0.02 Å and c = 2.47 ± 0.02 Å. The space group is determined to be Pnam. The angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 32.7°. Torsion of carbonyl group at this particular angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 0°. Hitherto this is the first time that a space group for aliphatic polyester of the type [-(CH2)n-CO-O-]x with even number of methylene units between successive ester groups is determined because poly-9-hydroxynonanoate is the first to show Bragg reflections on the non-equatorial layer line.","abstract_html":"Crystal structures of helical columnar pi-conjugated systems, namely helicene-bisquinone and dendronized perylene bisimide derivative as well as of a biodegradable aliphatic polyester, namely poly-9-hydroxynonanoate, have been resolved by means of fibre X-ray diffraction. Enantiopure and racemic helicene-bisquinones are found to be organized into columnar liquid crystalline phases. The internal structure of the columns is 132 hollow helix with the asymmetric unit comprised of six-molecules, hence of 78 molecules and two turns in a period of 112 Å. The long-range order among the columns is found to be laterally high but longitudinally - low. This is the first atomic-level determination of a helical columnar liquid crystalline phase. The crystal structure of N,N’-di-(3,4,5-dodecyloxy-oxyphenylethyl)-perylene bisimide is approximated by distorted helical columns arranged within an orthorhombic unit cell with lattice parameters a = 70.2 ± 0.02 Å, b = 41.1 ± 0.02 Å, and c = 45.5 ± 0.02 Å. The space group is determined to be P212121. The internal structure of the columns is approximated by 61 helices. The structure is based on four-molecule repeat units (tetramers). There are 24 molecules and two turns in a 45.51 Å period of the distorted 6-fold helix. The tetramer is comprised of 2 dimers (two boat-shaped molecules placed side-by-side) facing each other in the tetramer. The rotation angle between the dimers within the tetramer is 100°. Charge mobility along the columns has been found to depend critically on the detailed molecular packing. The crystal structure of poly-9-hydroxynonanoate is established to be polyethylene-like except that the ester groups are randomly distributed throughout the lattice. The molecular chain of poly-9-hydroxynonanoate is determined to possess planar zigzag conformation with two such chains arranged within an orthorhombic unit cell with lattice parameters, a = 7.47 ± 0.02 Å, b = 5.00 ± 0.02 Å and c = 2.47 ± 0.02 Å. The space group is determined to be Pnam. The angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 32.7°. Torsion of carbonyl group at this particular angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 0°. Hitherto this is the first time that a space group for aliphatic polyester of the type [-(CH2)n-CO-O-]x with even number of methylene units between successive ester groups is determined because poly-9-hydroxynonanoate is the first to show Bragg reflections on the non-equatorial layer line.","abstract_has_math":false,"creators":["Tadjiev, Timur"],"institution":"University of Sheffield","degree_name":"Ph.D","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Ungar, Goran"],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-08","date_published":"2011-08","updated_at":"2026-07-24T06:04:57Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["uk.bl.ethos.557443"],"render_values":[{"text":"uk.bl.ethos.557443","href":null,"code":true}]}]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Ungar, Goran"]},{"key":"dc:creator","label":"Author","values":["Tadjiev, Timur"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-08-12"]},{"key":"dc:date.issued","label":"Date","values":["2011-08"]},{"key":"dc:publisher.commercial","label":"Dc Publisher Commercial","values":["University of Sheffield"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Materials Science and Engineering (Sheffield)"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Sheffield"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://etheses.whiterose.ac.uk/id/eprint/1623/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["Ph.D"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["uk.bl.ethos.557443"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://etheses.whiterose.ac.uk/id/eprint/1623/2/Tadjiev%2C_Timur.docx"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Crystal structures of helical columnar pi-conjugated systems, namely helicene-bisquinone and dendronized perylene bisimide derivative as well as of a biodegradable aliphatic polyester, namely poly-9-hydroxynonanoate, have been resolved by means of fibre X-ray diffraction. Enantiopure and racemic helicene-bisquinones are found to be organized into columnar liquid crystalline phases. The internal structure of the columns is 132 hollow helix with the asymmetric unit comprised of six-molecules, hence of 78 molecules and two turns in a period of 112 Å. The long-range order among the columns is found to be laterally high but longitudinally - low. This is the first atomic-level determination of a helical columnar liquid crystalline phase. The crystal structure of N,N’-di-(3,4,5-dodecyloxy-oxyphenylethyl)-perylene bisimide is approximated by distorted helical columns arranged within an orthorhombic unit cell with lattice parameters a = 70.2 ± 0.02 Å, b = 41.1 ± 0.02 Å, and c = 45.5 ± 0.02 Å. The space group is determined to be P212121. The internal structure of the columns is approximated by 61 helices. The structure is based on four-molecule repeat units (tetramers). There are 24 molecules and two turns in a 45.51 Å period of the distorted 6-fold helix. The tetramer is comprised of 2 dimers (two boat-shaped molecules placed side-by-side) facing each other in the tetramer. The rotation angle between the dimers within the tetramer is 100°. Charge mobility along the columns has been found to depend critically on the detailed molecular packing. The crystal structure of poly-9-hydroxynonanoate is established to be polyethylene-like except that the ester groups are randomly distributed throughout the lattice. The molecular chain of poly-9-hydroxynonanoate is determined to possess planar zigzag conformation with two such chains arranged within an orthorhombic unit cell with lattice parameters, a = 7.47 ± 0.02 Å, b = 5.00 ± 0.02 Å and c = 2.47 ± 0.02 Å. The space group is determined to be Pnam. The angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 32.7°. Torsion of carbonyl group at this particular angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 0°. Hitherto this is the first time that a space group for aliphatic polyester of the type [-(CH2)n-CO-O-]x with even number of methylene units between successive ester groups is determined because poly-9-hydroxynonanoate is the first to show Bragg reflections on the non-equatorial layer line."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["Crystal Structures of Helical Columnar pi-Conjugated Systems and Biodegradable Polyester"]}]}],"canonical_facts":{"dc:contributor.advisor":["Ungar, Goran"],"dc:creator":["Tadjiev, Timur"],"dc:date":["2011-08-12"],"dc:date.issued":["2011-08"],"dc:description.abstract":["Crystal structures of helical columnar pi-conjugated systems, namely helicene-bisquinone and dendronized perylene bisimide derivative as well as of a biodegradable aliphatic polyester, namely poly-9-hydroxynonanoate, have been resolved by means of fibre X-ray diffraction. Enantiopure and racemic helicene-bisquinones are found to be organized into columnar liquid crystalline phases. The internal structure of the columns is 132 hollow helix with the asymmetric unit comprised of six-molecules, hence of 78 molecules and two turns in a period of 112 Å. The long-range order among the columns is found to be laterally high but longitudinally - low. This is the first atomic-level determination of a helical columnar liquid crystalline phase. The crystal structure of N,N’-di-(3,4,5-dodecyloxy-oxyphenylethyl)-perylene bisimide is approximated by distorted helical columns arranged within an orthorhombic unit cell with lattice parameters a = 70.2 ± 0.02 Å, b = 41.1 ± 0.02 Å, and c = 45.5 ± 0.02 Å. The space group is determined to be P212121. The internal structure of the columns is approximated by 61 helices. The structure is based on four-molecule repeat units (tetramers). There are 24 molecules and two turns in a 45.51 Å period of the distorted 6-fold helix. The tetramer is comprised of 2 dimers (two boat-shaped molecules placed side-by-side) facing each other in the tetramer. The rotation angle between the dimers within the tetramer is 100°. Charge mobility along the columns has been found to depend critically on the detailed molecular packing. The crystal structure of poly-9-hydroxynonanoate is established to be polyethylene-like except that the ester groups are randomly distributed throughout the lattice. The molecular chain of poly-9-hydroxynonanoate is determined to possess planar zigzag conformation with two such chains arranged within an orthorhombic unit cell with lattice parameters, a = 7.47 ± 0.02 Å, b = 5.00 ± 0.02 Å and c = 2.47 ± 0.02 Å. The space group is determined to be Pnam. The angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 32.7°. Torsion of carbonyl group at this particular angle between the C-C-C... zigzag plane of poly-9-hydroxynonanoate and the b-axis is determined to be 0°. Hitherto this is the first time that a space group for aliphatic polyester of the type [-(CH2)n-CO-O-]x with even number of methylene units between successive ester groups is determined because poly-9-hydroxynonanoate is the first to show Bragg reflections on the non-equatorial layer line."],"dc:format":["text"],"dc:identifier":["uk.bl.ethos.557443"],"dc:identifier.uri":["https://etheses.whiterose.ac.uk/id/eprint/1623/2/Tadjiev%2C_Timur.docx"],"dc:publisher.commercial":["University of Sheffield"],"dc:publisher.department":["Materials Science and Engineering (Sheffield)"],"dc:publisher.institution":["University of Sheffield"],"dc:relation.isreferencedby":["https://etheses.whiterose.ac.uk/id/eprint/1623/"],"dc:title":["Crystal Structures of Helical Columnar pi-Conjugated Systems and Biodegradable Polyester"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["Ph.D"]},"updated_at":"2026-07-24T06:04:57Z"}