論文 / 著書情報
Article / Book Information
題目(和文)

アントラセン環に囲まれた配位ナノ空間の特異なホスト機能

Title(English)

Unique Host Functions of Coordination Nanocavities Surrounded by
Anthracene Rings

著者(和文)

山科雅裕

Author(English)

Masahiro Yamashina

出典(和文)

学位:博士（工学）,学位授与機関:東京工業大学,
報告番号:甲第10216号,授与年月日:2016年3月26日,
学位の種別:課程博士,
審査員:吉沢 道人,穐田 宗隆,山元 公寿,河野 正規,竹内 大介

Citation(English)

Degree:,Conferring organization: Tokyo Institute of Technology,
Report number:甲第10216号,
Conferred date:2016/3/26,
Degree Type:Course doctor,
Examiner:,,,,

学位種別(和文)

博士論文

Category(English)

Doctoral Thesis

種別(和文)論文要旨

Type(English)

Summary

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The functions of organic and coordinative nanospaces have recently received much attention becauseof their synthetic designability, accessibility and adjustability. As mentioned above, unique properties andreactivities within synthetic molecular hosts have attracted considerable attention in the field of organic,
biological, physical, and material chemistry. Whereas a variety of organic and coordinative nanospace havebeen synthesized, most of the cavity frameworks are composed of aliphatic units and/or small aromatic rings.
Coordination molecular hosts bearing organic ligands with extended polyaromatic panels remain uncommon.
Thus, I presumed that molecular capsules with large coordinative nanospace encircled by polyaromatic
frameworks could generate novel guest behaviors through efficient host-guest interactions.
Through this thesis, I challenged to investigate unique host-guest phenomena within enclosed
polyaromatic nanocavities for the purpose of exploring unusual molecular recognition and photophysicalproperties. As a polyaromatic nanospece, I employed M2L4 coordination molecular capsules, which have alarge cavity (~1 nm in diameter and ~580 Å3 in volume) surrounded by eight anthracene rings tightly. It has
been revealed that the Pd(II)- or Pt(II)-linked capsules can encapsulate simple, hydrophobic, and rigidorganic compounds such as fullerene C60, corannulene, and pyrene through effective hydrophobic effects andaromatic-aromatic interactions between host frameworks and guest molecules. However, unusual guest
recognition, conformation, structure, properties, and reactivities have not been explored so far in thenanospace.
The selective recognition of male sex hormones over female ones was successfully demonstrated byusing the Pt(II)-linked polyaromatic capsule in water. Competitive binding experiments revealed that thecapsule preferentially binds male hormones through multiple CH-π interactions between the hormones andthe capsule frameworks. Furthermore, fluorescent detection of steroid hormones was achieved by using ahost-guest complex with a fluorescent dye.
I disclosed that sucrose, a highly hydrophilic disaccharide, was successfully encapsulated in thewell-defined cavity of the Pt(II)-linked polyaromatic capsule in water. Through the efficient host-guestinteractions, the capsule displayed selective and excellent host capability for sucrose with a binding constant(Ka) of 2.9 × 103 M–1 at ambient temperature.
Unlike previous coordinative host-guest systems, highly emissive host-guest complexes (up to ΦF =50%) were successfully prepared upon encapsulation of various fluorescent dyes (e.g., BODIPY andcoumarin derivatives) by the Pt(II)-linked coordination capsule in water. Picosecond time-resolved
spectroscopy elucidated the photophysical behaviors of the obtained complexes. Notably, the emission colorof the fluorescent the host-guest complex containing the BODIPY derivative could be readily modulated
upon pairwise encapsulation with planar aromatic molecules.

The well-known and widely used radical initiators such as AIBN (2,2’-azobisisobutyronitrile) and its
derivatives were successfully stabilized toward external stimuli through encapsulation within thePd(II)-linked nanocapsule with polyaromatic frameworks. The encapsulation process occurred quantitatively
by hydrophobic host-guest interactions in aqueous solution at room temperature. The encapsulated initiators
within the capsule were significantly stabilized against light irradiation (580 times) and heat (645 times). The
safely stored initiators could be used for usual olefin polymerization in organic solvent through spontaneous
release of the initiators.
Oligo(ethylene oxide)s (OEO) are well-known highly hydrophilic compounds but were quantitativelyenclathrated in the hydrophobic cavity of the Pt(II)-linked polyaromatic nanocapsule in water. The
hydrophilic long-chain compounds were quantitatively enclathrated in the hydrophobic cavity of the capsule.
Depending on the length of OEOs, the bounded molecules formed coiled or pseudo-rotaxane-shapedconformations. In addition, selective encapsulation of oligo(ethylene oxide)s was demonstrated by using thecapsule.
Anisotropic expansion of the spherical M2L4 coordination capsule through the elongation of the ligand
led to a new M2L’4 capsule. The expanded capsule provides an elliptical cavity encircled by polyaromatic
frameworks with large openings and thereby could encapsulate elliptical fullerene C70 andmonofunctionalized fullerene C60 in high yields. In addition, selective formation of a new M2L2L’2 capsuleoccurred by mixing the original M2L4 and expanded M2L’4 capsules in a 1:1 ratio upon addition of C60 ormono-functionalized C60 as a template molecule.
Through above works, I have developed new chemical functions and phenomena within polyaromatic
nanocapsules through effective host-guest interactions. I realized that the isolated cavities fully encircled bypolyaromatic frameworks capable of (i) encapsulating various organic molecules, (ii) showing highmolecular recognition capability, (iii) inducing unusual fluorescent properties, and (iv) stabilizing reactive
chemical reagents toward light and heat, which cannot be achieved by previous molecular cages andcapsules. These results would greatly progress host-guest chemistry and also contribute to the design of a
new type of molecular sieves, sensors, probes, and reactors and the investigation of their furtherdevelopments and applications.	 	 	 	 	 9430	 	 3:082-/BG9#3<9F=F2H@@5ELF<BH?869FH6@=GG98=A9=G<9E57BCLB:  ,5C5A9F9&<5E57G9EF5A84BE8F(A;{=F<BE7BCLB:!
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