{"created":"2023-06-20T13:21:26.359919+00:00","id":1651,"links":{},"metadata":{"_buckets":{"deposit":"8a5e02bc-6c7a-4efc-b502-1aaf313b4d6f"},"_deposit":{"created_by":21,"id":"1651","owners":[21],"pid":{"revision_id":0,"type":"depid","value":"1651"},"status":"published"},"_oai":{"id":"oai:ir.soken.ac.jp:00001651","sets":["2:427:9"]},"author_link":["0","0","0"],"item_1_creator_2":{"attribute_name":"著者名","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"小田, 雅文"}],"nameIdentifiers":[{}]}]},"item_1_creator_3":{"attribute_name":"フリガナ","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"オダ, マサフミ"}],"nameIdentifiers":[{}]}]},"item_1_date_granted_11":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2010-03-24"}]},"item_1_degree_grantor_5":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_name":"総合研究大学院大学"}]}]},"item_1_degree_name_6":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士（理学）"}]},"item_1_description_12":{"attribute_name":"要旨","attribute_value_mlt":[{"subitem_description":" The supramolecular integration of porphyrin and its derivatives has attracted
to obtain well-defined porphyrin aggregates, not only covalent bonding but also metal
coordination, hydrogen-bonding and van der Waals interactions have been utilized
and the obtained integrated structures have been employed for applications in various
fields of materials science and technology. I have focused on the supramolecules of
amphiphilic motives with rigid π-conjugated cores, which have been well employed to
obtain excellent optoelectronic properties associated with the characteristic
nanostructures. In this study, I have developed an asymmetrically β-substituted
amphiphilic porphyrin, which is designed to be much planar and less bulky with an
aim to accomplish densely packed nanostructures and induce strong intermolecular
interactions between the metal centers.
The triethyleneglycol(TEG)-tethered and alkyl-tethered dipyrromethanes have
been prepared, and then the synthesis of the target porphyrin has been accomplished
by the condensation reaction of these dipyrromethanes. In contrast to the synthesis
of meso-aryl-type porphyrin, that of asymmetrically substituted β-alkyl-type
porphyrin has not been well explored. Several conditions were examined for the
condensation reaction of two different dipyrromethanes and finally, the target zinc
porphyrin was successfully obtained by condensation of TEG-tethered dipyrromethane
and an alkyl-tethered α,α’-dipropylimino-dipyrromethane in refluxing cyclohexane in
the presence of Zn(OAc)22H2O as a template. In this procedure, an isomerization
reaction of porphyrin derivatives, so-called scrambling reaction, was suppressed under
lower reaction temperature or in less polar solvents by hampering the pathway of this
side-reaction. For the optimized synthesis, 44.8 mg of the porphyrin mixture was
obtained in 18% yield and the ratio of the target compound and the isomer
(isomer/target) was 0.03. The isolation of the target porphyrin 1-Zn from the
isomeric mixture was accomplished by repeated recrystallizations from the solution
in a CH2Cl2-MeOH mixed solvent. As a result, the isomeric mixture of 44.8 mg afforded
22.5 mg of the target 1-Zn to be pure at NMR level. The characterization of the
target porphyrin has been carried out by 1H and 13C NMR spectroscopies and HR
FAB-MS spectrometry. The central zinc atom was demetallated under the acidic
condition with TFA in CH2Cl2 and the freebase porphyrin 1-H2 was obtained in 98%
yield. The insertion of copper ions was carried out by refluxing the solution of 1-H2
in the presence of Cu(OAc)2・H2O, which resulted in target compound 1-Cu
quantitatively.
The supramolecular integration of the obtained porphyrins 1-H2 and 1-Cu has been
examined in some polar solvents by taking advantageous of the amphiphilic properties
of the porphyrins. The UV-Vis spectral changes were observed on adding H2O to the
solution of the freebase 1-H2 in THF. The Soret absorption band of 1-H2 shows red shift
by 42 nm. Similar behaviors were observed for the absorption experiments of 1-H2
upon cooling the hot MeOH solution. On the other hand, when H2O was added to the
solution of 1-Cu in THF, the Soret band of 1-Cu at 397 nm displayed clear blue shifts
with a peak (λmax) at 392 nm in THF : H2O = 1 : 9 mixed solvent. In general, Kasha’
s exciton theory predicts that a blue shift observed in the optical absorption indicates a
face-to-face H-aggregation of the chromophores.
The shapes of the nanostructures of the integrated porphyrin assemblies have been
confirmed by the SEM and TEM observations. When the suspension of freebase
porphyrin 1-H2 precipitated from the hot MeOH solution was casted on a substrate, the
TEM image revealed a rod structure that consists of the bundles of wires with the
diameter of about 25 nm. The precipitate of 1-Cu obtained from THF-H2O showed short
rod-like structures with the diameter of around 11 nm and the length in the range of
140－310 nm as estimated from the SEM and TEM observations. The SEM image of
the precipitate of 1-Cu obtained from a hot MeOH solution afforded a helical
ribbon-structure without chiral selectivity.
The XRD analysis of the precipitate of 1-Cu from THF-H2O solution revealed that
the molecules are packed in a monoclinic unit cell with the dimensions of a = 67.71(4), b
= 3.546(3) and c = 24.62(2) Åand β = 96.72(7)° and the π-stacked 1-D chains are aligned to the b-axis with the π-stacking distance of 3.55 Å.
I investigated the thermal magnetic behaviors of 1-Cu with SQUID measurements
in order to confirm the intermolecular metal-metal interaction induced by the
supramolecular integration. The magnetic susceptibility of the precipitate obtained
from THF-H2O solution shows a bent on decreasing temperature, which indicates a weak magnetic interaction between the Cu(II) centers. The Curie-Weiss plot of the
susceptibility between 4-300 K affords the Weiss constant as -0.22 K. The induction of
intermolecular magnetic interaction between metal centers with soft-material systems is
rare.
The supramolecular integration of the porphyrin without any solvents has been also
investigated by slow cooling from the melting state. The DSC measurement and the
POM observation of 1-Cu showed that the melting point was ca. 130 ℃ and the
porphyrin was thermally stable upto this temperature region. When 1-Cu was heated
over 130 ℃, fluid-like porphyrin was observed. After cooling to r. t., integrated 1-Cu
was obtained easily and the UV-Vis spectrum and the XRD analysis of this aggregate
suggested a similar supramolecular structure as 1-Cu precipitates obtained from the
solution in polar solvents.
In summary, I have succeeded in the syntheses of novel amphiphilic porphyrin
complexes, investigated their self-assembly behaviors and the properties of the
assembled nanostructures.","subitem_description_type":"Other"}]},"item_1_description_18":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_1_description_7":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_description":"総研大甲第1313号","subitem_description_type":"Other"}]},"item_1_select_14":{"attribute_name":"所蔵","attribute_value_mlt":[{"subitem_select_item":"有"}]},"item_1_select_8":{"attribute_name":"研究科","attribute_value_mlt":[{"subitem_select_item":"物理科学研究科"}]},"item_1_select_9":{"attribute_name":"専攻","attribute_value_mlt":[{"subitem_select_item":"07 構造分子科学専攻"}]},"item_1_text_10":{"attribute_name":"学位授与年度","attribute_value_mlt":[{"subitem_text_value":"2009"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"ODA, Masafumi","creatorNameLang":"en"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2016-02-17"}],"displaytype":"simple","filename":"甲1313_要旨.pdf","filesize":[{"value":"342.6 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"要旨・審査要旨","url":"https://ir.soken.ac.jp/record/1651/files/甲1313_要旨.pdf"},"version_id":"31b88a0d-8328-4aec-9a59-422648c0f91a"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2016-02-17"}],"displaytype":"simple","filename":"甲1313_本文.pdf","filesize":[{"value":"37.2 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"本文","url":"https://ir.soken.ac.jp/record/1651/files/甲1313_本文.pdf"},"version_id":"a2cf70eb-ab64-4439-9d6b-b777ec2baa0f"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"thesis","resourceuri":"http://purl.org/coar/resource_type/c_46ec"}]},"item_title":"Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes"},{"subitem_title":"Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes","subitem_title_language":"en"}]},"item_type_id":"1","owner":"21","path":["9"],"pubdate":{"attribute_name":"公開日","attribute_value":"2011-01-14"},"publish_date":"2011-01-14","publish_status":"0","recid":"1651","relation_version_is_last":true,"title":["Synthesis and Supramolecular Assembly of Highly Planar Amphiphilic Porphyrin Complexes"],"weko_creator_id":"21","weko_shared_id":-1},"updated":"2023-06-20T15:54:18.512542+00:00"}