Nanotechnologies / Materials
Sensing, Energy conversion, Molecular seiving

Development of multicomponent covalentorganic!"#$%&'()
frameworks*+,$%!"#$%&'289*!"#$%&'$()*!"#":;<=>()=?@7+,-./01234567!"#!

Division of Applied Chemistry, Graduate School of EngineeringhNO $%& $ijklg%&' " "\ABC& ! "JXmnop
Associate Professor Mitsuharu Suzuki

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https://researchmap.jp/-ms?lang=en%&'"

ABC&Abstract▍ Significance of the research and Future perspective

component COFs.

Viewing multicomponent COFs as “solid solutions” greatly enhances their structural design possibilities. This study aims to develop intricate functional materials that efficiently realize complex
processes, such as energy conversion and multistep catalysis, bycontinuously tuning composition and lattice constants while maintaining crystallinity.

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G/3'+8:)6'30'-3=)6'*()'
1003(=)()='+3'*4+)(-*+)

E32*4'=,63(=)(6')F,6+',-'-3=)'*((*-.)5)-+80$3-J)-+,3-*4*-= -)/ :,2+1()6 30 514+,235:3-)-+ $%&6>KF)5:4,0,)=/,+9+9) "@-3=)L!@4,-I)( 9)F*.3-*4 686+)5>60

Intensity (a.u.)

While most of the reported COFs have simple compositions
involving only one or two types of monomers, there have been
an increasing number of reports regarding multicomponent systems in recent years. A few examples have already been foundwhereincrease in thenumber of components
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E,-I)( brings about uniqueproperties. However, it is not clear whether multicomponent COFs
低高エントロピー
possess regularly
ordered monomer sequences
as expected; accordingly, the detailed investigation of structure–property correlaの設計にエントロピー工学などの概念を持ち込み，新たな高tions has scarcely progressed. Furthermore, many aspects remain
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unresolved regarding the requirements for forming multicomponent
COFs.
In view of this background, we are investigating the influence ofthe physical and chemical properties of monomers on the formationof multicomponent COFs, as well as elucidating the structure of resulting COFs. As a part of the project, this work thoroughly examined
twelve ternary systems composed of monomers with different phys!"#$%&'()*"&+,-&.$/,-)(&,01,02"0(&,03-$%&'()*"
ical dimensions and chemicalreactivities. The results revealed thefollowing aspects regarding theexamined hexagonal 2D COFs: (1)G/3'+8:)6'30'-3=)6'*()'
E32*4'=,63(=)(6')F,6+'
ternary COFs adopt a solid-solution-likestructure that encompasses
3(=)()='+3'*4+)(-*+),-'-3=)'*((*-.)5)-+
local disorders in monomer sequences and the resulting distortions;$3-J)-+,3-*4*-=COFs-)/ are:,2+1()630 only514+,235:3-)-+$%&6>(2) ternary
obtained
when such distortions
are tolerKF)5:4,0,)=+9) "@-3=)L!@4,-I)(
9)F*.3-*4
ated; /,+9otherwise,a mixture of twotypes of 686+)5>
binary COFs is produced;and (3) the difference in reactivity between the combined monomers has a limited influence on the feasibility of 3-component COF
formation. Accumulation of this kind of knowledge must lead clear
enable effective structuraldesign of multicomponent
Low guidelines thatEntropy
HighCOFs. Furthermore, the solid-solution-type structures have hardly
examinedin organic
crystals;thus, theof thisng new beenfunctionalorganic
materials
by bringing
in achievements
thestudy
present
anewfrontierinorganic
materials.
pt of “entropy engineering” into the design ofH3=)'"402000 20 40 60 80 100
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8

特定の要件を満たす 3 成分 COF では，固溶体のように組成（左）ìîï3456789と格子定数（右）を連続的に調整することができる．
!"#$$()*+,-. -)/ 01-2+,3-*4 3(.*-,2 5*+)(,*46 78 7(,-.,-. ,- +9)23-2):+ 30 ;)-+(3:8 )-.,-))(,-.< ,-+3 +9) =)6,.- 30514+,235:3-)-+ $%&6>
10080
60
40
2000 20 40 60 80 100
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78In some three-component COFs, it is feasible to continuously
adjust the composition (left) and lattice constants (right) as insolid solutions.

P a t e n tSuzuki, Mitsuharu; Nakayama, Ken-ichi et al. Possibilities and limitations in monomer combinations for ternary two-dimensional covalent organicT r e a t i s e frameworks. Journal of the American Chemical Society 2023, 145 (5), 3008–3015. doi: 10.1021/jacs.2c11520
URL
K e y w o r d covalent organic frameworks, porous crystals, solid solution

7

Intensity (a.u.)▍ Background & Results

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Inclusion of Node 1 (mol%)Nanotechnologies / Materials

Covalent Organic Frameworks (COFs) are crystalline porous polymers formed through covalent bonds between organic building
blocks. Due to their high structural order and exceptional porosity,COFs are considered for various applications including gas storage and separation, sensing, and catalysis. Multicomponent COFs,in particular, 主要図2
are garnering significant attention due to their remarkable design flexibility, encompassing both structural diversity andproperty variations. With this in mind, we are working on the designand structural control of multicomponent COFs based on a new*+,$%!"#$%&'()
perspectiveof considering themas “solid solutions.” The structural
depiction of solid solutions!"#$%&'$()*
differs significantly from the conven!"#$%&'289*
tional hypothesis that multicomponent COFs are formed as highly:;<=>()=?@7+,-./01234567
symmetrical and stable structures. This calls for the establishmentof new
design concepts"andsynthetic chemical
methodologies.
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Inclusion of Node 1 (mol%)%&'!