{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21859"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21859","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Porphyrins and metalloporphyrins as field-responsive materials","abstract":"{\\it Part I}. {\\it Metalloporphyrin coordination polymers}. One-dimensional coordination polymers of metalloporphyrins with non-symmetric bridging ligands have been synthesized as candidates for molecular ferroelectric materials. These include the iron(II) porphyrinate polymer: \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$ (where TPP = 5,10,15,20-tetraphenylporphyrinate(2$-$); pyCn = 4-cyanopyridine); iron(III) porphyrinate polymers: \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-MeIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-PhIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ (where 4-MeIm = 4-methylimidazolate; 4-PhIm = 4-phenylimidazolate; pyCO$\\sb2\\sp-$ = pyridine-4-carboxylate; OpyCO$\\sb2\\sp-$ = pyridine-4-carboxylate N-oxide; ImPhO$\\sp-$ = 4-(imidazol-1-yl)phenoxide); tin(IV) porphyrinate polymers: \\lbrack Sn$\\sp{\\rm IV}$(TPP)(ntp)\\rbrack$\\sb\\infty$ and \\lbrack Sn$\\sp{\\rm IV}$(TPP)(cnp)\\rbrack$\\sb\\infty$ (where ntp = nitroterephthalate; cnp = 4-carboxyl-2-nitrophenoxide). The single-crystal X-ray structures were solved for \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. The chain alignment of the bridging ligand is disordered in \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, anti-parallel in \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$ and \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, but polar in \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ crystallizes in a non-centrosymmetric space group, $Pna2\\sb1$.","abstract_html":"{\\it Part I}. {\\it Metalloporphyrin coordination polymers}. One-dimensional coordination polymers of metalloporphyrins with non-symmetric bridging ligands have been synthesized as candidates for molecular ferroelectric materials. These include the iron(II) porphyrinate polymer: \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$ (where TPP = 5,10,15,20-tetraphenylporphyrinate(2$-$); pyCn = 4-cyanopyridine); iron(III) porphyrinate polymers: \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-MeIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-PhIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ (where 4-MeIm = 4-methylimidazolate; 4-PhIm = 4-phenylimidazolate; pyCO$\\sb2\\sp-$ = pyridine-4-carboxylate; OpyCO$\\sb2\\sp-$ = pyridine-4-carboxylate N-oxide; ImPhO$\\sp-$ = 4-(imidazol-1-yl)phenoxide); tin(IV) porphyrinate polymers: \\lbrack Sn$\\sp{\\rm IV}$(TPP)(ntp)\\rbrack$\\sb\\infty$ and \\lbrack Sn$\\sp{\\rm IV}$(TPP)(cnp)\\rbrack$\\sb\\infty$ (where ntp = nitroterephthalate; cnp = 4-carboxyl-2-nitrophenoxide). The single-crystal X-ray structures were solved for \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. The chain alignment of the bridging ligand is disordered in \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, anti-parallel in \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$ and \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, but polar in \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ crystallizes in a non-centrosymmetric space group, $Pna2\\sb1$.","abstract_has_math":true,"creators":["Chen, Chin-Ti"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Kenneth S. Suslick"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:21:21Z","date_published":"2011-05-07T13:21:21Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Inorganic","Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1992 Chen, Chin-Ti"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236420","(UMI)AAI9236420"],"render_values":[{"text":"AAI9236420","href":null,"code":true},{"text":"(UMI)AAI9236420","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21859","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Kenneth S. Suslick"]},{"key":"dc:creator","label":"Author","values":["Chen, Chin-Ti"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:21:21Z","10000-01-01","1992"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic","Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1992 Chen, Chin-Ti"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236420","(UMI)AAI9236420","http://hdl.handle.net/2142/21859"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["{\\it Part I}. {\\it Metalloporphyrin coordination polymers}. One-dimensional coordination polymers of metalloporphyrins with non-symmetric bridging ligands have been synthesized as candidates for molecular ferroelectric materials. These include the iron(II) porphyrinate polymer: \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$ (where TPP = 5,10,15,20-tetraphenylporphyrinate(2$-$); pyCn = 4-cyanopyridine); iron(III) porphyrinate polymers: \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-MeIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-PhIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ (where 4-MeIm = 4-methylimidazolate; 4-PhIm = 4-phenylimidazolate; pyCO$\\sb2\\sp-$ = pyridine-4-carboxylate; OpyCO$\\sb2\\sp-$ = pyridine-4-carboxylate N-oxide; ImPhO$\\sp-$ = 4-(imidazol-1-yl)phenoxide); tin(IV) porphyrinate polymers: \\lbrack Sn$\\sp{\\rm IV}$(TPP)(ntp)\\rbrack$\\sb\\infty$ and \\lbrack Sn$\\sp{\\rm IV}$(TPP)(cnp)\\rbrack$\\sb\\infty$ (where ntp = nitroterephthalate; cnp = 4-carboxyl-2-nitrophenoxide). The single-crystal X-ray structures were solved for \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. The chain alignment of the bridging ligand is disordered in \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, anti-parallel in \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$ and \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, but polar in \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ crystallizes in a non-centrosymmetric space group, $Pna2\\sb1$.","Pressed pellets of \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ gave no detectable ferroelectric hysteresis in polarization. Calculations based on the crystal structure of \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ shows that the bulky structure of the porphyrin ring significantly limits the magnitude of the spontaneous polarization.","{\\it Part II}. {\\it Push-pull porphyrins as nonlinear optical materials}. ``Push-pull'' porphyrins, $\\rm H\\sb2(a\\sb{x}n\\sb{4-x}Por),$ (where x = 1--4; a = {\\it p\\/}-aminophenyl; n = {\\it p\\/}-nitrophenyl; Por = 5,10,15,20-substituted porphyrin) has been synthesized and characterized by various physical methods. Their second-order non-linear optical properties have been measured by the EFISH technique giving substantial $\\beta$ in the range 10 to 30 $\\times$ 10$\\sp{-30}$ {\\it esu\\/} (1.91 $\\mu$m, CHCl$\\sb3$).","Moderate to strong solvatochromic effects have been observed in several {\\it cis\\/} isomers of ``push-pull'' porphyrins, H$\\sb2$({\\it cis\\/}-a$\\sb2$n$\\sb2$Por), H$\\sb2$\\lbrack{\\it cis\\/}-(Ocda)n$\\sb2$Por\\rbrack, and H$\\sb2$\\lbrack{\\it cis\\/}-h$\\sb2$(Ocdpy)$\\sb2$Por\\rbrack(I)$\\sb2$ \\lbrack where Ocda = {\\it p\\/}-(N-octadecylamino)phenyl; h = {\\it p\\/}-hydroxyphenyl; Ocdpy = {\\it p\\/}-(N-octadecyl)pyridiniumyl\\rbrack. $\\sp1$H NMR can detect the non-symmetric ring current in {\\it cis\\/} isomers of ``push-pull'' porphyrins. The relative polarization of the $\\pi$-electron cloud can be ordered as H$\\sb2$\\lbrack{\\it cis\\/}$\\sb2$-h$\\sb2$(Ocdpy)$\\sb2$Por\\rbrack$\\sp{2+}$ $\\sim$ H$\\sb2$\\lbrack{\\it cis\\/}-m$\\sb2$(Mpy)$\\sb2$Por\\rbrack$\\sp{2+}$ $>$ H$\\sb2$\\lbrack{\\it cis\\/}-(Ocda)$\\sb2$n$\\sb2$Por\\rbrack \\ $>$ H$\\sb2$({\\it cis\\/}-a$\\sb2$n$\\sb2$Por) $>$ H$\\sb2$({\\it cis\\/}-h$\\sb2$py$\\sb2$Por) $\\sim$ H$\\sb2$({\\it cis\\/}-m$\\sb2$py$\\sb2$Por) $>$ H$\\sb2$\\lbrack{\\it cis\\/}-({\\it s\\/}-Clprmd)$\\sb2$n$\\sb2$Por\\rbrack\\ $\\sim$ H$\\sb2$\\lbrack{\\it cis\\/}-(Ocdmd)$\\sb2$n$\\sb2$Por\\rbrack \\ (where Mpy = {\\it p\\/}-N-methylpyridiniumyl; py = 4-pyridyl; m = {\\it p\\/}-methoxyphenyl; {\\it s\\/}-Clprmd = {\\it p\\/}-({\\it s\\/}-2-chloropropinoylamido)phenyl; Ocdmd = {\\it p\\/}-octadecanoylamidophenyl\\rbrack.","The isotherms of amphiphilic porphyrins, {\\it i.e.\\/}, H$\\sb2$\\lbrack(Ocdmd)$\\sb{\\rm x}$n$\\sb{\\rm 4-x}$Por\\rbrack, were studied. We found that porphyrins with one or two aliphatic substituents (x = 1 or 2) adopt a perpendicular orientation to the water surface with the mean molecular area ($A\\sb0$) less than 120 \\AA$\\sp2$; those with three or four aliphatic substituents (x = 3 or 4) have a parallel orientation to the water surface with $A\\sb0$ larger than 190 \\AA$\\sp2$. $A\\sb0$ of H$\\sb2$\\lbrack{\\it cis\\/}-(Ocdmd)$\\sb2$n$\\sb2$Por\\rbrack, H$\\sb2$\\lbrack{\\it cis\\/}-(Ocda)n$\\sb2$Por\\rbrack, and H$\\sb2$\\lbrack{\\it cis\\/}-h$\\sb2$(Ocdpy)$\\sb2$Por\\rbrack(NO$\\sb3)\\sb2$, was found to be 112 $\\pm$ 5, 108 $\\pm$ 5, and 142 $\\pm$ 5 \\AA$\\sp2$, respectively, in Langmuir films.","Made available in DSpace on 2011-05-07T13:21:21Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236420.pdf: 11357105 bytes, checksum: a58029931ac98994f6ff16977f10a7c8 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:41Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:51-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Porphyrins and metalloporphyrins as field-responsive materials"]}]}],"canonical_facts":{"dc:contributor":["Kenneth S. Suslick"],"dc:creator":["Chen, Chin-Ti"],"dc:date":["2011-05-07T13:21:21Z","10000-01-01","1992"],"dc:description":["{\\it Part I}. {\\it Metalloporphyrin coordination polymers}. One-dimensional coordination polymers of metalloporphyrins with non-symmetric bridging ligands have been synthesized as candidates for molecular ferroelectric materials. These include the iron(II) porphyrinate polymer: \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$ (where TPP = 5,10,15,20-tetraphenylporphyrinate(2$-$); pyCn = 4-cyanopyridine); iron(III) porphyrinate polymers: \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-MeIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(4-PhIm)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ (where 4-MeIm = 4-methylimidazolate; 4-PhIm = 4-phenylimidazolate; pyCO$\\sb2\\sp-$ = pyridine-4-carboxylate; OpyCO$\\sb2\\sp-$ = pyridine-4-carboxylate N-oxide; ImPhO$\\sp-$ = 4-(imidazol-1-yl)phenoxide); tin(IV) porphyrinate polymers: \\lbrack Sn$\\sp{\\rm IV}$(TPP)(ntp)\\rbrack$\\sb\\infty$ and \\lbrack Sn$\\sp{\\rm IV}$(TPP)(cnp)\\rbrack$\\sb\\infty$ (where ntp = nitroterephthalate; cnp = 4-carboxyl-2-nitrophenoxide). The single-crystal X-ray structures were solved for \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$, \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, and Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. The chain alignment of the bridging ligand is disordered in \\lbrack Fe$\\sp{\\rm II}$(TPP)(pyCN)\\rbrack$\\sb\\infty$, anti-parallel in \\lbrack Fe$\\sp{\\rm III}$(TPP)(pyCO$\\sb2$)\\rbrack$\\sb\\infty$ and \\lbrack Fe$\\sp{\\rm III}$(TPP)(OpyCO$\\sb2$)\\rbrack$\\sb\\infty$, but polar in \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$. \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ crystallizes in a non-centrosymmetric space group, $Pna2\\sb1$.","Pressed pellets of \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ gave no detectable ferroelectric hysteresis in polarization. Calculations based on the crystal structure of \\lbrack Fe$\\sp{\\rm III}$(TPP)(ImPhO)\\rbrack$\\sb\\infty$ shows that the bulky structure of the porphyrin ring significantly limits the magnitude of the spontaneous polarization.","{\\it Part II}. {\\it Push-pull porphyrins as nonlinear optical materials}. ``Push-pull'' porphyrins, $\\rm H\\sb2(a\\sb{x}n\\sb{4-x}Por),$ (where x = 1--4; a = {\\it p\\/}-aminophenyl; n = {\\it p\\/}-nitrophenyl; Por = 5,10,15,20-substituted porphyrin) has been synthesized and characterized by various physical methods. Their second-order non-linear optical properties have been measured by the EFISH technique giving substantial $\\beta$ in the range 10 to 30 $\\times$ 10$\\sp{-30}$ {\\it esu\\/} (1.91 $\\mu$m, CHCl$\\sb3$).","Moderate to strong solvatochromic effects have been observed in several {\\it cis\\/} isomers of ``push-pull'' porphyrins, H$\\sb2$({\\it cis\\/}-a$\\sb2$n$\\sb2$Por), H$\\sb2$\\lbrack{\\it cis\\/}-(Ocda)n$\\sb2$Por\\rbrack, and H$\\sb2$\\lbrack{\\it cis\\/}-h$\\sb2$(Ocdpy)$\\sb2$Por\\rbrack(I)$\\sb2$ \\lbrack where Ocda = {\\it p\\/}-(N-octadecylamino)phenyl; h = {\\it p\\/}-hydroxyphenyl; Ocdpy = {\\it p\\/}-(N-octadecyl)pyridiniumyl\\rbrack. $\\sp1$H NMR can detect the non-symmetric ring current in {\\it cis\\/} isomers of ``push-pull'' porphyrins. The relative polarization of the $\\pi$-electron cloud can be ordered as H$\\sb2$\\lbrack{\\it cis\\/}$\\sb2$-h$\\sb2$(Ocdpy)$\\sb2$Por\\rbrack$\\sp{2+}$ $\\sim$ H$\\sb2$\\lbrack{\\it cis\\/}-m$\\sb2$(Mpy)$\\sb2$Por\\rbrack$\\sp{2+}$ $>$ H$\\sb2$\\lbrack{\\it cis\\/}-(Ocda)$\\sb2$n$\\sb2$Por\\rbrack \\ $>$ H$\\sb2$({\\it cis\\/}-a$\\sb2$n$\\sb2$Por) $>$ H$\\sb2$({\\it cis\\/}-h$\\sb2$py$\\sb2$Por) $\\sim$ H$\\sb2$({\\it cis\\/}-m$\\sb2$py$\\sb2$Por) $>$ H$\\sb2$\\lbrack{\\it cis\\/}-({\\it s\\/}-Clprmd)$\\sb2$n$\\sb2$Por\\rbrack\\ $\\sim$ H$\\sb2$\\lbrack{\\it cis\\/}-(Ocdmd)$\\sb2$n$\\sb2$Por\\rbrack \\ (where Mpy = {\\it p\\/}-N-methylpyridiniumyl; py = 4-pyridyl; m = {\\it p\\/}-methoxyphenyl; {\\it s\\/}-Clprmd = {\\it p\\/}-({\\it s\\/}-2-chloropropinoylamido)phenyl; Ocdmd = {\\it p\\/}-octadecanoylamidophenyl\\rbrack.","The isotherms of amphiphilic porphyrins, {\\it i.e.\\/}, H$\\sb2$\\lbrack(Ocdmd)$\\sb{\\rm x}$n$\\sb{\\rm 4-x}$Por\\rbrack, were studied. We found that porphyrins with one or two aliphatic substituents (x = 1 or 2) adopt a perpendicular orientation to the water surface with the mean molecular area ($A\\sb0$) less than 120 \\AA$\\sp2$; those with three or four aliphatic substituents (x = 3 or 4) have a parallel orientation to the water surface with $A\\sb0$ larger than 190 \\AA$\\sp2$. $A\\sb0$ of H$\\sb2$\\lbrack{\\it cis\\/}-(Ocdmd)$\\sb2$n$\\sb2$Por\\rbrack, H$\\sb2$\\lbrack{\\it cis\\/}-(Ocda)n$\\sb2$Por\\rbrack, and H$\\sb2$\\lbrack{\\it cis\\/}-h$\\sb2$(Ocdpy)$\\sb2$Por\\rbrack(NO$\\sb3)\\sb2$, was found to be 112 $\\pm$ 5, 108 $\\pm$ 5, and 142 $\\pm$ 5 \\AA$\\sp2$, respectively, in Langmuir films.","Made available in DSpace on 2011-05-07T13:21:21Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236420.pdf: 11357105 bytes, checksum: a58029931ac98994f6ff16977f10a7c8 (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:41Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:51-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9236420","(UMI)AAI9236420","http://hdl.handle.net/2142/21859"],"dc:language":["eng"],"dc:rights":["Copyright 1992 Chen, Chin-Ti"],"dc:subject":["Chemistry, Inorganic","Chemistry, Organic"],"dc:title":["Porphyrins and metalloporphyrins as field-responsive materials"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:18Z"}