Wa e So p ion Ho Pape
Consecu i e Single-C ys al- o-Single-C ys al Isome iza ion o No el
Oc amolybda e Anions wi hin a Mic opo ous Hyb id F amewo k
wi h Robus Wa e So p ion P ope ies
Es ibaliz Ruiz-Bilbao, Amaia I u ospe, San iago Reinoso, Beña A e xe,*
Ga ikoi z Beobide, Lei e San Felices, Luis Lezama, Juan M. Gu ié ez-Zo illa,
Shaza Da wish, Debob o o Sensha ma, and Michael J. Zawo o ko
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Angewand e
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Abs ac : The 3D hyb id amewo k [{Cu(cyclam)}3(k-
Mo8O27)]·14H2O (1) (cyclam=1,4,8,11- e aazacyclo e-
adecane) unde goes sequen ial single-c ys al- o-single-
c ys al ans o ma ions upon hea ing o a o d wo
di e en anhyd ous phases (2a and 3a). These ansi-
ions modi y he amewo k dimensionali y and enable
he isome iza ion o k-oc amolybda e (k-Mo8) anions
in o λ(2a) and μ (3a) o ms h ough me al mig a ion.
Hyd a ion o 3a in ol es condensa ion o one wa e
molecule o he clus e o a o d he γ-Mo8isome in 4,
which dehyd a es back in o 3a h ough he 6a in e -
media e. In con as , 2a e e sibly hyd a es o o m 5,
exhibi ing he same Mo8clus e as ha o 1. I is
ema kable ha h ee o he Mo8clus e s (k,λand μ)
a e new and ha up o h ee di e en mic opo ous
phases can be isola ed om 1(2a,3a, and 6a). Wa e
apo so p ion analyses show high ecyclabili y and he
highes up ake alues o POM-based sys ems. The
iso he ms display an ab up s ep a low humidi y le el
desi able o humidi y con ol de ices o wa e ha es -
ing in d ylands.
In oduc ion
The de elopmen o po ous ma e ials wi h capaci y o adso b
gases and apo s ep esen s a po en ial solu ion o cu en
global challenges such as a mosphe ic pollu ion[1] and sca ci y
o eshwa e .[2] Indeed, a mosphe ic wa e ha es ing no
only has he po en ial o add ess he global wa e sho age
c isis, bu also p o ides oppo uni ies o ab ica e p ac ical
de ices o wa e pu i ica ion,[3] dehumidi ica ion,[4] o indoo
humidi y con ol.[5] In his sense, Me al-O ganic F amewo ks
(MOFs) a e highly p omising ma e ials o gas so p ion and
sepa a ion,[6–7] because hei modula cons i u ion allows he
ine- uning o po e size and chemis y. Howe e , wa e
so p ion could be challenging due o he limi ed hyd oly ic
s abili y displayed by some MOF amilies.[8–9] Inco po a ion
o igid, ino ganic building-blocks ha expose elec onega i e
a oms owa d he amewo k po es migh imp o e he
s abili y and selec i i y owa d pola adso ba es like wa e .[10]
In he pas ew yea s, polyoxome ala e (POM)-based
po ous c ys alline solids[11–12] ha e a ac ed g ea a en ion
due o he possibili y o combining he in insic mul i unc ion-
ali y o hese clus e s (e.g. ca alysis, magne ism, o
luminescence)[13] wi h he p ope ies o ex ended open- ame-
wo k a chi ec u es. Insoluble ionic c ys als in which disc e e
me al-o ganic mac oca ions a e combined wi h Keggin- ype
he e oPOMs [XW12O40]n(X=CoII, BIII, SiIV, PV)[14] ha e
exhibi ed selec i e wa e so p ion p ope ies,[15–16] because he
non-e icien packing o such mac o-ionic en i ies ende s
meaning ul po osi y o he s uc u e. Ano he s a egy
in ol es he assembly o POMs wi h ansi ion me al
complexes ac ing as linke s. Some o us ecen ly s udied he
use o CuII complexes o mac ocyclic polyamines in which
equa o ial posi ions on he me al cen e a e blocked by he
mul iden a e ligand, lea ing axial posi ions a ailable o
linking con iguous POM uni s. This app oach led o di e en
mul i unc ional ma e ials, including he obus
sup amolecula amewo k [Cu(cyclam)][{Cu(cyclam)}2-
(V10O28)]·10H2O (cyclam=1,4,8,11- e aazacyclo e ade-
cane), which selec i ely adso bs CO2o e N2and ca alyzes
he he e ogeneous oxida ion o adaman ane,[17] as well as he
[{Cu(cyclam)}3(W7O24)]·15.5H2O co alen hyb id wi h gas
so p ion capaci y and he abili y o unde go he mally-
igge ed single-c ys al- o-single-c ys al (SCSC)
ans o ma ions.[18]
SCSC ans o ma ions allow o moni o ing and gaining
insigh in o how he loca ion o a oms and molecules a ies
du ing a solid-s a e phase ansi ion. The s uc u al changes
induced by ex e nal s imuli may modi y key p ope ies o he
pa en s uc u e (e.g. magne ic, op ical, o adso p i e) and
lead o applica ions in sensing, selec i e s o age, and molec-
ula swi ches, among o he s. Fu he mo e, SCSC ans o ma-
ions can a o d compounds showing peculia a chi ec u es
di e en om hose ob ained by con en ional syn he ic
ou es.
Al hough his p ope y is di icul o achie e wi hou he
ma e ial losing c ys allini y, ens o examples o SCSC ans-
o ma ions ha e been epo ed o da e o coo dina ion
ne wo ks.[19] In compa ison, examples a e sca ce o POM-
based sys ems,[20] despi e he ac ha he la ges change in a
cell olume (ca. 2170 Å3) obse ed o such kind o ans-
o ma ion co esponds o a sol en -media ed ansi ion o he
Li9K7WCo10[H2P8W48O186] sal .[21] The ela i e a angemen o
POM uni s o coun e ions is usually modi ied du ing hese
[*] E. Ruiz-Bilbao, D . B. A e xe, D . G. Beobide, P o . L. Lezama,
P o . J. M. Gu ié ez-Zo illa
Depa amen o de Química O gánica e Ino gánica, Facul ad de
Ciencia y Tecnología, Uni e sidad del País Vasco UPV/EHU
P.O. Box 644, 48080 Bilbao (Spain)
E-mail: [email p o ec ed]
D . A. I u ospe
Cen o de Física de Ma e iales (CSIC, UPV/EHU)
Paseo Manuel La dizabal 5, 20018 Donos ia-San Sebas ián (Spain)
D . S. Reinoso
Depa amen o de Ciencias & Ins i u e o Ad anced Ma e ials and
Ma hema ics (InaMa 2), Uni e sidad Pública de Na a a (UPNA)
Campus de A osadia, 31006 Pamplona (Spain)
D . G. Beobide, P o . J. M. Gu ié ez-Zo illa
BCMa e ials
Edi icio Ma ina Casiano, 3 d Floo , UPV/EHU Science Pa k, Ba io
Sa iena s/n, 48940 Leioa (Spain)
D . L. San Felices
Se icios Gene ales de In es igación SGIke , Facul ad de Ciencia y
Tecnología, Uni e sidad del País Vasco UPV/EHU
P.O. Box 644, 48080 Bilbao (Spain)
D . S. Da wish, D . D. Sensha ma, P o . M. J. Zawo o ko
Be nal Ins i u e, Depa men o Chemical Sciences, Uni e si y o
Lime ick
Lime ick V94 T9PX (I eland)
© 2023 The Au ho s. Angewand e Chemie In e na ional Edi ion
published by Wiley-VCH GmbH. This is an open access a icle unde
he e ms o he C ea i e Commons A ibu ion Non-Comme cial
NoDe i s License, which pe mi s use and dis ibu ion in any med-
ium, p o ided he o iginal wo k is p ope ly ci ed, he use is non-
comme cial and no modi ica ions o adap a ions a e made.
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Angew. Chem. In . Ed. 2023,62, e202307436 (2 o 9) © 2023 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH
15213773, 2023, 42, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202307436 by Uni e sidad Del Pais Vasco, Wiley Online Lib a y on [15/12/2023]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
solid s a e eac ions,[22] bu no majo skele al modi ica ion o
he me al-oxo clus e has been obse ed o da e wi h he
excep ion o i) an alkylammonium sal o [γ-SiV2W10O39]4,
which ans o ms i s linea (μ-oxo)-di anadium(V) co e in o
a bis(μ-hyd oxo)-di anadium moie y when exposed o
mois u e;[23] and ii) he isome iza ion o [B-H2As2Mo6O26-
(H2O)]4 o [A-H2As2Mo6O26]4wi hin a POM/me al–o ganic
amewo k.[24]
The la e example belongs o ou sys ema ic s udies on
he {Cu(cyclam)}2+/POM amily, which has p o en sui able
o p epa ing hyb id coo dina ion ne wo ks able o unde go
SCSC ans o ma ions.[25] As pa o ou con inuing in es-
iga ions on he in e ac ion be ween {Cu(cyclam)}2+and
isopolymolybda es,[26] he e we epo he hyb id coo dina ion
ne wo k [{Cu(cyclam)}3(k-Mo8O27)]·14H2O (1), which con-
ains a no el oc amolybda e (Mo8) clus e (labeled k) and
unde goes sequen ial, he mally-induced SCSC ans o ma-
ions o a o d wo di e en anhyd ous phases (2a and 3a).
Beyond ele an ea angemen o he CuO bonding
scheme, hese ansi ions in ol e isome iza ion o k-Mo8in o
λ(2a) and μ (3a) o ms h ough mig a ion o Mo cen e s
wi h a ia ion o hei coo dina ion numbe s. The h ee Mo8
clus e s a e no el, he eby enla ging he ca alog o as many as
9 di e en isome s epo ed o da e.[27–29] The e e sibili y o
hese phase ansi ions has been s udied and wa e apo
so p ion p ope ies analyzed o he mic opo ous phases 2a
and 3a.
Resul s and Discussion
Compound 1was i s ob ained as a pu ple c ys alline powde
in ca. 15% yield om he eac ion o comme cial (NH4)6-
[Mo7O24] and he in si u p epa ed {Cu(cyclam)}2+complex
(1:3 s oichiome ic a io) in wa e a pH=6.5, ollowed by
addi ion o 1,4-dioxane. Samples sui able o single-c ys al X-
ay di ac ion (SCXRD) we e al e na i ely ob ained by using
hyd o he mal me hods. The in a ed spec um and powde
X- ay di ac ion (PXRD) pa e n o he esul ing p isma ic
c ys als bo h i well wi h hose ob ained o he polyc ys al-
line samples (Figu es S1–S3). Fo a mo e de ailed Expe -
imen al Sec ion, see he Suppo ing In o ma ion.
Mo i a ed by he wide he mal s abili y ange (ca. 100–
230°C) ound in he he mog a ime ic (TGA) cu e o 1
upon dehyd a ion (Figu es S4–S5), a iable empe a u e
(VT) PXRD pa e ns we e eco ded om oom empe a u e
(RT) o 600°C e e y 20°C (Figu e S6) o explo e i s he mo-
s uc u al beha io , i.e. whe he 1shows c ys allini y e en-
ion o e amo phiza ion wi h inc easing empe a u e, and in
he o me case, whe he i displays amewo k dynamism s
obus ness. Resul s e ealed ha he hyb id coo dina ion
ne wo k e ains c ys allini y h oughou he whole dehyd a-
ion p ocess and beyond up o 230°C, in line wi h he he mal
s abili y ange ound in he TGA cu e. Upon hea ing, 1
apidly ans o ms in o a new c ys alline phase (2a) as
indica ed by majo modi ica ions in bo h posi ions and
ela i e in ensi ies o he main di ac ion peaks. In pa icula ,
he wo in ense maxima a 2θ=7.1°and 7.4°posi ions in 1
spli in o h ee di e en signals loca ed a 7.3, 7.5, and 7.7°in
2a (Figu e S7). Mo eo e , he peak a 10.5° anishes and new
signals appea a 11.3, 22.5, and 23.2°. Conside ing ha his
ans o ma ion akes place a alues close o RT, addi ional
PXRD pa e ns we e collec ed om 30 o 46°C e e y 2°C o
explo e his phase ansi ion in dep h (Figu e S8). These
expe imen s e ealed ha 2a is al eady ully o med a 36°C,
and acco ding o he TGA esul s, should co espond o a
pa ially dehyd a ed phase. Howe e , no mass loss associa ed
wi h he elease o H2O molecules was obse ed in he TGA
analyses ca ied ou o a sample o 1p e iously kep a 40°C
o 1 h o ensu e i s ull con e sion in o 2a. These obse a-
ions sugges slow kine ics go e ning he emo al o gues
sol en molecules om 1, and con i m he anhyd ous na u e
o 2a. Phase 2a emains s able un il 110°C, bu unde goes an
addi ional ansi ion abo e his empe a u e, ans o ming
in o a high- empe a u e anhyd ous phase (3a), as indica ed
by he eme gence o a new pai o mos in ense maxima a
7.4 and 7.8°wi h app ox. 3:1 in ensi y a io.
SCXRD da a (Table S1) show ha 1c ys allizes in he
monoclinic space g oup P21/nwi h an asymme ic uni (ASU)
con aining one [k-Mo8O27]6anion (k-Mo8), a o al o h ee
{Cu(cyclam)}2+complexes, o which wo (Cu1A, Cu1B) a e
loca ed in gene al posi ions and ano he wo on cen e s o
symme y (Cu1C, Cu2C), and 14 H2O molecules diso de ed
o e 20 si es (Figu e S9). The k-Mo8anion is no el, he eby
enla ging he cu en ca alog o Mo8clus e s in he li e a u e
(Table S2). I can be bes desc ibed as one {Mo4O16} e ame
and one {Mo3O13} ime used by sha ing one ace and one
co ne be ween MoO6oc ahed a, wi h he eigh h Mo cen e
exhibi ing squa e py amidal geome y. The la e is connec ed
o he e ame by edge-sha ing and o he ime by sha ing
wo co ne s (Figu e 1a). To ou knowledge, he Mo8species
epo ed o da e comp ise up o nine di e en s uc u al
isome s o he [Mo8O26]4anion, namely α,β,γ,δ,ɛ,ζ,η,θ
and ι,[27–29] and a single isome ic o m (γ) o he {Mo8O28}6
coun e pa . The la e is a building block ha can be ound
s abilized ei he by p o ona ion in he [Mo8O26(OH)2]6
anion,[30] o by polyme iza ion,[26] esul ing in {Mo8O27}nand
{Mo8O26}nchain-like assemblies depending on he numbe o
co ne s sha ed o polyme ize. Despi e he a ie y o MoOx
uni s (x=4–6) and polyhed al connec i i y shown in Table S2
o Mo8isome s, he ace-sha ing ea u e o k-Mo8is
s uc u ally no el.
All CuII cen e s display oc ahed al CuN4O2geome y wi h
cyclam N a oms in equa o ial posi ions and e minal OPOM
a oms occupying bo h axial posi ions. Signi ican Jahn–Telle
dis o ion is p esen in all complexes, wi h he longes
Cu1AOPOM bond leng h o 2.876(5) Å being close o semi-
coo dina ion (Table S3). The c ys al packing (Figu e S10)
e eals a 3-dimensional po ous coo dina ion ne wo k, in
which hyb id laye s o k-Mo8clus e s linked o ou neighbo s
h ough ou b idging complexes (Cu1A, Cu1B, Cu1C,
Cu2C) can be iden i ied in he (1�
10) plane (Figu e 1b). This
pa e n esul s in hombus-like g ids wi h wo ypes o oids
a anged al e na ely along he c ys allog aphic zaxis. These
g ids a e u he connec ed h ough coo dina ion o wo
addi ional complexes (Cu1Ai, Cu1Bii; symme y codes in
Figu e S10) o a o d an open- amewo k a chi ec u e in
which mul iple CH···OPOM and NH···OPOM con ac s es ab-
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lished be ween cyclam ligands and POM su aces play a
ele an ein o cing ole (Table S4). The s uc u e exhibi s a
3-dimensional sys em o in e sec ed, wa e - illed channels
wi h ca i ies loca ed a he space be ween 8 neighbo ing
clus e s and connec ed h ough na ow necks de ined by 4
neighbo ing complexes (Figu e 1c). The channels un along
he [001], [1�
10] and [110] di ec ions, hei necks show c oss-
sec ions o ca. 9.7×9.1 and 9.6×9.2 Å (in e a omic dis ances
be ween opposi e N a oms o he g id oids), and hei o al
sol en accessible space accoun s o 32% o he uni cell
olume.
To explo e he s uc u al changes ha he he mally-
igge ed ansi ions abo e imply, SCXRD expe imen s we e
conduc ed on c ys als o 1hea ed o 1 h a 50 and 120°C o
ensu e ull ans o ma ion in o he anhyd ous 2 a and 3a
phases, espec i ely. Fo 2a, dehyd a ion esul s in a dec ease
o he uni cell olume o less han one-hal o ha o 1, which
is associa ed wi h he educ ion o he cell symme y o he
iclinic P�
1space g oup. The ASU (Figu e S11) now con ains
one [λ-Mo8O27]6(λ-Mo8) clus e and a o al o h ee {Cu-
(cyclam)}2+moie ies: one loca ed in gene al posi ions (Cu1C)
and ou hal es o cen osymme ic complexes (Cu1A, Cu2A,
Cu1B, Cu2B).
The Mo8clus e unde goes k o λisome iza ion du ing
he phase ansi ion. This isome iza ion implies up u e o he
ace-sha ing connec ion be ween {Mo4O16} and {Mo3O13}
agmen s obse ed in he k o m and o ma ion o he edge-
sha ing {Mo6O22} moie y exhibi ed by he new λ- ype anion,
which is simila o he cap displayed by he well-known [β-
Mo8O26]8species (Figu e 2a). This ea angemen p oceeds
ia he up u e o wo Mo-μ3O bonds and he ollowing
consequen modi ica ions: i) he se en h {MoO6} oc ahed on
goes om exclusi ely sha ing edges in he k o m o
exclusi ely sha ing co ne s in he λisome , and ii) he eigh h
Mo cen e dec eases i s coo dina ion numbe om i e o
ou ( e ahed al geome y) and becomes linked o each o
he agmen s abo e by sha ing one co ne . Thus, solid-s a e
mig a ions o some o he Mo cen e s ake place wi hin he
clus e skele on (Table S5 and Suppo ing Mo ies).
Rega ding he c ys al packing, hyb id laye s in he (01�
1)
plane a e analogous o hose desc ibed o 1bu now he
hombus-like g id shows wo oid ypes o dis inc size: hose
delimi ed by Cu1B and Cu1C, which a e compa able in size
o he oids in 1(9.2×9.4 Å), and hose de ined by Cu2A and
Cu1C wi h much smalle dimensions o 7.5×8.6 Å (Figu e 2b).
The connec ion be ween shee s is also di e en om ha in 1
because only hal o he {Cu(cyclam)}2+moie ies loca ed in
he in e lamella space e ain elonga ed oc ahed al geome y
(Cu2B), whe eas he o he hal becomes squa e plana
(Figu es S12–S13). The la e Cu1A complexes lose hei
cha ac e as co alen linke s, bu s ill play a signi ican ole in
s abilizing he s acking o hyb id g ids by es ablishing hyd o-
gen bonding connec i i y wi h e ame ic aces o λ-Mo8
clus e s om adjacen shee s (Figu e S12, Table S4). The
connec ion be ween in e lamella ca i ies loca ed a he space
among clus e s is dis up ed h ough cons ic ions in ol ing
Cu1A and Cu2A agmen s; hence, he 3-dimensional
sol en -accessible ne wo k ound in 1is disman led in 2a.
Figu e 1. a) Polyhed al iew o [k-Mo8O27]6(k-Mo8) ({Mo4O16}
e ame , pink; {Mo3O13}, ligh blue; {MoO5}, g ay). b) P ojec ion o a
hyb id laye o 1on he (1�
10) plane ({MoO5} polyhed a o k-Mo8, da k
g ay; {CuN4O2} oc ahed a, blue; OWa oms, ed sphe es). c) Su ace
ep esen a ion o in e connec ed wa e - illed channels in 1.
Figu e 2. a) Polyhed al iew o he λ-Mo8isome ({Mo6O22} hexame ,
lilac; se en h {MoO6}, pink; e ahed al {MoO4}, g ay). b) P ojec ion o
a hyb id laye o 2a on he (01�
1) plane. c) Polyhed al iew o he μ-Mo8
isome ({Mo7O24} hep ame , ligh g ay; e ahed al {MoO4}, da k g ay).
d) P ojec ion o a sup amolecula laye o 3a on he (101) plane.
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The esul ing ca i ies ne e heless emain connec ed h ough
s ings o al e na e wide and na owe windows a anged
along he yaxis in a zig-zag mode, gi ing ise o a po ous
sys em o pa allel channels ha diagonally in e sec he
s acking o hyb id laye s (Figu e S14). These po es a e emp y
in 2a and co espond o 24% o he uni cell olume.
The second high- empe a u e anhyd ous phase (3a)
c ys allizes in he same space g oup as 1wi h he ASU
(Figu e S15) o med by one [μ-Mo8O27]6(μ-Mo8) clus e ,
wo {Cu(cyclam)}2+moie ies in gene al posi ions (Cu1A,
Cu1B), and ano he wo hal es o cen osymme ic com-
plexes (Cu2A, Cu1C). The phase ansi ion om 2a o 3a
in ol es u he isome iza ion o he Mo8clus e om he λ
o he new μ o m (Figu e 2c). This p ocess implies ull edge-
sha ing condensa ion o he se en h {MoO6} uni in he λ
isome o he hexame ic cap, esul ing in a {Mo7O24} agmen
analogous o ha displayed by [β-Mo8O26]8. As a esul , he
eigh h Mo cen e becomes a e ahed al {MoO4} an enna uni
a ached by a single co ne -sha ing linkage. I is no ewo hy
ha he h ee Mo8isome s epo ed in his wo k a e no el,
e idencing ha solid-s a e ans o ma ions can a o d POMs
ha canno be accessed by con en ional sol en -media ed
syn he ic ou es.
Compa ed o 1and 2a, he co alen 3-dimensional
ne wo k is b oken in 3a, because he in alamella moie y
Cu1B loses i s linking cha ac e and becomes a pen acoo di-
na e appended uni wi h squa e-py amidal geome y. Con-
e sely, complexes Cu2A and Cu1C e ain hei b idging ole
in such a way ha he μ-Mo8anions a e co alen ly linked in o
zig-zagging ibbons along he yaxis (Figu e 2d). The
appended complexes ne e heless s ill play a key ole in
assembling such ibbons in o sup amolecula hyb id laye s in
he (101) plane h ough a massi e hyd ogen bonding ne wo k
wi h he e ame ic aces o μ-Mo8clus e s (Figu e S16,
Table S4). The s acking o hese sup amolecula assemblies is
acili a ed by in e lamella Cu1A complexes, which in con-
as o wha obse ed o 2a, a e all oc ahed al co alen
linke s (Figu e S17). The po ous ne wo k in 3a consis s also
o a sys em o pa allel channels, bu in his case, he
in e lamella ca i ies appea connec ed along he s acking
[101] di ec ion ia he wide necks wi h ca. 8.6×8.4 Å c oss-
sec ion ha he o ma ion o he pen acoo dina e appended
uni s opens. These emp y po es accoun o 23% o he uni
cell olume.
To s udy he e e sibili y o he SCSC ansi ions abo e,
samples o 2a and 3a we e exposed o he labo a o y
a mosphe e (LA: 15–20°C; 40–50% ela i e humidi y, RH)
and moni o ed by a combina ion o TGA and PXRD. Wi h
espec o 3a, TGA analyses eco ded a e 1, 3, and 7 d o
ai exposu e (Figu es S18–S19) e ealed ha he anhyd ous
phase cap u es up o 12 H2O molecules pe POM a e one
week (%m, calcd 9.8; ound 9.6), o which as many as 10 a e
adso bed du ing he i s 24 h. No addi ional H2O molecules
we e adso bed a e 7 d o ai exposu e and he hyd a ion/
dehyd a ion cycles in he esul ing samples p o ed o be ully
e e sible. These esul s a e in line wi h hose om PXRD
s udies, which indica e ha a new c ys alline phase (4)
di e en om he pa en 1s a s o ming when 3a hyd a es,
bu i is no ully o med un il he se en h day o ai exposu e
(Figu e S20). In an a emp o p omo e a as e ans o ma-
ion, c ys als o 3a we e placed in a mo e humid a mosphe e
and addi ional PXRD analyses demons a ed ha o ma ion
o 4could each comple ion in jus 24 h (Figu e S21). In
con as , soaking he c ys als in wa e o 1 h appea ed o
imply sligh deg ada ion, as e idenced by some addi ional
poo ly esol ed maxima ound in he expe imen al di ac ion
pa e ns (Figu e S22). The e e sibili y o such ansi ion was
co obo a ed h ough VT-PXRD on 4(Figu e S23), which
showed an in e media e phase (6a) in he ansi ion om 4 o
3a a 120°C upon hea ing.
Conside ing he in ica e c ys al dynamics shown by his
sys em, we es ed whe he he s uc u e o 4could be
elucida ed by SCXRD. Fo una ely, he da a acqui ed on a
c ys al o 3a exposed o ai o 7 days we e sui able o a ull
s uc u al esolu ion. Unluckily, we we e no able o collec
any da a se o good quali y o he in e media e 6a despi e
es ing se e al di e en c ys al ba ches. Compound [{Cu-
(cyclam)}3{γ-Mo8O26(OH)2}]·11H2O (4) c ys allizes in he
iclinic P�
1space g oup and i s ASU con ains one-hal o he
well-known {γ-Mo8O26(OH)2}6species,[30] h ee hal es o
c ys allog aphically independen {Cu(cyclam)}2+moie ies and
5.5 H2O molecules o e 9 si es (Figu e S24).
Fo ma ion o [γ-Mo8O26(OH)2]6in 4(Figu e 3a) implies
ha one H2O molecule condenses o he POM skele on and
u he dissocia es along he hyd a ion p ocess. P o ona ion
si es ha e been unequi ocally assigned on he basis o Bond
Valence Sum calcula ions (Table S6).[31] The isome iza ion o
he Mo8anion o he mo e condensed, he modynamically
a o ed γ o m a e a ull dehyd a ion-phase ansi ion-
Figu e 3. a) Polyhed al iew o [γ-Mo8O26(OH)2]6(p o ona ed O a oms,
ma oon sphe es). b) P ojec ion o a hyb id laye o 4on he (001)
plane. c) Su ace ep esen a ion o in e connec ed wa e - illed channels
in 4.
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hyd a ion cycle sugges s ha all he h ee p e ious isome s in
1,2a and 3a a e ob ained only because o he s abiliza ion
p o ided by he hyd ogen bonding ne wo k es ablished
be ween cyclam ligands and su ace OPOM a oms. Indeed,
hese weak bu coope a i e o ces, oge he wi h he plas ici y
o CuII cen e s, migh well be he key ac o in allowing such
a s ing o consecu i e SCSC ans o ma ions in his
sys em.[22]
The ans o ma ion o 3a in o 4upon hyd a ion implies
ha all {Cu(cyclam)}2+moie ies egain hei oc ahed al
geome y and b idging ole. Thus, each γ-Mo8uni is
connec ed o six neighbo s o gi e ise o a 3-dimensional
co alen ne wo k eminiscen o ha o 1in which hyb id
g ids wi h squa e-like oids o c oss-sec ion 9.1×9.0 Å s ack
along he [001] di ec ion (Figu es 3b, S25). As in 1, his
a chi ec u e is pie ced by a sys em o in e connec ed channels
along he h ee c ys allog aphic axes ha hos all he H2O
molecules (Figu e 3c). The necks ha communica e he wide
ca i ies a he space be ween 8 neighbo ing clus e s a e
somewha na owe han hose in 1, hence he sol en -
accessible space is sligh ly educed o oughly 30% o he
uni cell olume.
In con as o 3a, hyd a ion o 2a upon ai exposu e was
ully achie ed in jus 24 h (Figu es S19, S26). Nei he he
numbe o adso bed H2O molecules calcula ed om TGA,
no he PXRD pa e ns o he esul ing samples, ma ched any
o he p e ious c ys alline phases. This con i ms he i e e -
sibili y o he ansi ion om he pa en hyd a ed phase 1 o
he low- empe a u e anhyd ous de i a i e 2a. In ac , VT-
PXRD pa e ns eco ded e e y 2°C o he cooling p ocess o
2a om 46 o 30°C showed ha a new phase (5) s a s
o ming a RT wi hin he expe imen al ime-scale (Fig-
u e S27). The ansi ion om 2a o 5is ully e e sible as
indica ed by PXRD analyses ca ied ou o 5when hea ing
om 30 o 100°C e e y 5°C (Figu e S28).
The s uc u e o he new hyd a ed phase 5was de e -
mined on c ys als o 2a exposed o LA o 24 h o ensu e ull
hyd a ion. Compound [{Cu(cyclam)}3(k-Mo8O27)]·13H2O (5)
c ys allizes in he iclinic P�
1space g oup wi h one k-Mo8
anion, a o al o h ee {Cu(cyclam)}2+complexes (Cu1B in
gene al posi ion; Cu1A, Cu2B, Cu1C, and Cu2C on cen e s
o in e sion), and 13 H2O molecules o e 16 si es in he ASU
(Figu e S29). I is no ewo hy ha 5exhibi s he same k-Mo8
isome as 1, hence he k o λisome iza ion ha akes place
when going om 1 o 2a is e e sible despi e such phase
ansi ion being i e e sible. On he o he hand, 5displays
he same space g oup as 2 a wi h e y simila uni cell
pa ame e s, and he e o e, his hyd a ed phase migh be
iewed as a ansien s a e be ween pa en 1and anhyd ous
2a. In ac , p elimina y expe imen s on he c ys al dynamics
igge ed by acuum in his sys em show ha 5gene a es
upon dehyd a ion o 1in hese condi ions and subsequen
pa ial hyd a ion. Fu he s udies on his ma e will be
epo ed in due cou se.
Rega ding he c ys al packing, he a angemen o POMs
and b idging complexes wi hin he hyb id laye s in 5is
i ually iden ical o ha in 2a (Figu e S30), bu wi h he wo
dis inc g id oids somewha enla ged (9.1×8.7 and 9.6×9.4 Å)
p obably due o he b ea hing e ec p o ided by he
inco po a ion o H2O molecules. In con as o 2a, no squa e-
plana complexes a e ound in he in e lamella space as he
s acking o hyb id laye s along he [01�
1] di ec ion is
exclusi ely due o oc ahed al complex linke s. The esul ing
open amewo k displays a 2-dimensional in e lamella sys-
em o in e wined channels unning along he [011] and [100]
di ec ions ha hos all H2O molecules. These sol en -
accessible egions a e connec ed along he s acking di ec ion
only h ough he wide g id oids de ined by Cu1B and Cu2C
(Figu e S31), accoun ing o 29% o he uni cell olume.
Figu e 4 summa izes he in ica e he mally-induced c ys al
dynamics shown by he i le {Cu(cyclam)}2+/Mo8sys em and
he collec ion o SCSC ansi ions ha ela e he i e c ys al
phases desc ibed in his wo k.[32]
Conside ing ha 1 e ains mic opo osi y upon he mal
emo al o gues H2O molecules, and ha he po e windows
a e a p io i wide enough o enable he di usion o small
molecule adso ba es, he gas so p ion p ope ies o he wo
di e en anhyd ous phases in his wo k we e e alua ed.
Figu e 5 displays he esul s om N2(77 K) and CO2(195 K)
so p ion expe imen s ca ied ou on c ys alline samples o 1
ac i a ed a 50 and 120°C unde acuum o ensu e ull
con e sion in o 2a and 3a, espec i ely.
The N2adso p ion cu es co espond o ype Ia iso he ms
ypical o mic opo ous ma e ials wi h na ow po es (<1 nm).
In bo h cases, mic opo es a e illed apidly a low ela i e
p essu es (p/p0<0.1) o achie e sa u a ion ha ex ends up o
p/p0=1. The maximum gas up ake alues o 2a and 3a (72
and 76 cm3(STP) g1, espec i ely) accoun o 6.4 and 6.8
adso bed N2molecules pe Mo8uni . The adso p ion
p ocesses we e obse ed o be comple ely e e sible, and
hence, all he gas molecules a e deso bed a p/p0=0. Fi ing
o bo h adso p ion b anches o he B unaue –Emme –Telle
(BET) model[33] a o ds simila alues o BET su ace a eas
o 2a and 3a (302 and 298 m2g1). Al hough hese alues a e
much lowe han he highes a eas epo ed o POM-loaded
MOFs (>1000 m2g1),[34–35] ou esul s a e compa able o
hose displayed by some o he POM-me alo ganic ame-
wo ks, such as [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]
(205 m2g1),[16] o (TBA)2[Cu(BBTZ)2(α-Mo8O26)]
Figu e 4. Scheme o he SCSC ans o ma ions epo ed in his wo k.
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(773 m2g1; BBTZ=1,4-bis(1,2,4- iazol-1-ylme hyl)-
benzene).[36]
In ega d o he CO2up ake iso he ms, sa u a ion is
oughly achie ed a much highe ela i e p essu es (p/p0=
1.0). The adso p ion p ocesses we e also obse ed o be ully
e e sible and he maximum up akes we e also ound o
each e y simila alues o 2a and 3a (66 and 64 cm3
(STP) g1), accoun ing o 5.9 and 5.7 adso bed CO2mole-
cules pe Mo8uni . In con as o wha we obse ed in ela ed
POM/Cu(cyclam) po ous amewo ks, in which N2adso p ion
was negligible[16] o he maximum up ake accoun ed o only
30% o he simula ed alue,[17] bo h N2and CO2a e eadily
adso bed by 2a and 3a. This ac encou aged us o ca y ou
addi ional expe imen s a di e en empe a u es o gain a
be e unde s anding o he adso p i e p ope ies o such
anhyd ous phases and o es hei pe o mance in pu i ica-
ion o selec i e cap u e o small molecule gas mix u es.
These esul s will be epo ed elsewhe e in due cou se.
The e e sible na u e o he ansi ions om 2a o 5and
om 3a o 4mo i a ed us o s udy he wa e - apo so p ion
p ope ies o ou he mally-ac i a ed mic opo ous ma e ials.
Dynamic apo so p ion (DVS) expe imen s we e conduc ed
a 298 K om acuum o 90% RH o bo h anhyd ous
phases. Fo 2a, he adso p ion iso he m indica es ha po es
emain i ually emp y up o almos 20% o RH. A e his
poin , a sudden inc ease o he wa e up ake occu s wi h a
s eep s ep ha eaches ca. 70% o he o al capaci y a 35%
RH. The maximum up ake a 90% RH ep esen s an
inc ease o 16.4% o he o al mass wi h espec o ha o 2a
(Figu e 6a). Small di e ences be ween he calcula ed mass
o he 13 H2O molecules in he esul ing hyd a ed phase 5
and he alues ound expe imen ally (Table S7) could a ise
om he su ace condensa ion ha can ake place in he
in e g anula space.[2] These alues esul in a maximum
wo king capaci y o 222 cm3g1 o 2a, which is one o he
highes alues obse ed o da e o POM-based wa e
so ben s (see Table S8 o li e a u e up ake alues o ela ed
compounds and associa ed discussion, including a b ie
compa ison o zeoli es and MOFs). The deso p ion p ocess is
almos supe imposable o he adso p ion, which sugges s ull
e e sibili y. In o de o con i m i s cyclabili y, a second
iso he m was measu ed unde he same condi ions and he
wo king capaci y emained i ually iden ical (218 cm3g1,
16.2% change in mass a 90% RH). PXRD analyses on 2 a
e i ied e en ion o c ys allini y a e he adso p ion/deso p-
ion p ocesses (Figu e S32).
Wi h espec o 3a, his phase does no adso b any
signi ican amoun o wa e below 15% RH. F om his poin ,
a s eep wa e up ake is obse ed up o 35% RH, a e which
he slope o he adso p ion p o ile dec eases. This slowe s ep
ex ends up o 50% RH and accoun s o he mass o a single
H2O molecule. This obse a ion could esul om he
s uc u al ansi ion om 3a o 4associa ed wi h he
inco po a ion o one H2O molecule o he POM skele on and
subsequen s uc u al ea angemen om [μ-Mo8O27]6 o [γ-
Mo8O26(OH)2]6(Figu e 6b). A e eaching a maximum
wo king capaci y o 235 cm3g1(17.4% change in mass) a
90% RH, he deso p ion p ocess sugges s ha he [γ-Mo8O26-
(OH)2]6anion emains s able upon dehyd a ion because one
H2O molecule is e ained in he ac i e ma e ial. PXRD
analyses (Figu e S33) con i med ha 4does no e e back
o 3a unde acuum and indica e ha he hi d anhyd ous
phase (6a) could be gene a ed as a esul . The PXRD pa e n
o his phase i s well wi h ha obse ed o a sample o 4
ea ed unde acuum (Figu e S34), as well as, o ha o he
in e media e phase ound in he he mal ansi ion om 4 o
3a upon hea ing (Figu e S23). FTIR spec a sugges he
p esence o he γ-Mo8isome in 6a, albei inconclusi ely
(Figu e S35). The dis inc adso p ion/deso p ion p ocesses
made us eco d addi ional cycles (Figu e 6c). The e e sibili y
o he wa e up ake be ween phases 4and 6a was con i med
because bo h cu es we e i ually iden ical and hey showed
a maximum wo king capaci y o 223 cm3g1a 90% RH
(16.5% change in mass).
Besides he o al capaci y, he cyclabili y o he sys em
and so p ion kine ics a e also impo an ac o s ha should
be aken in o accoun o u ili y. Conside ing ha i) he s eep
up ake akes place a 20–35% RH ange in all cases, and ii)
80% o he o al capaci y is eached a 60% RH (s anda d
wo king condi ions o some common comme cial
Figu e 5. N2and CO2iso he ms o a) 2a and b) 3a. Filled and emp y
ma ke s co espond o adso p ion and deso p ion b anches, espec-
i ely.
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desiccan s),[37] he kine ics o hese wo p ocesses we e s udied
a a cons an apo low a e o 30 and 60% RH, espec i ely.
Unde low humidi y apo low swing (0–30–0% RH), wa e
up ake ook as long as 100 min o be comple ed (Figu -
es S36–S37), whe eas bo h adso p ion and deso p ion p oc-
esses a e achie ed in less han 15 min a a RH swing o 0–60–
0% o bo h phases a RT.
The du abili y and ecyclabili y o he adso ben s we e
e alua ed by 100 cycles o wa e adso p ion-deso p ion
expe imen s a 298 K and a cons an apo low a e o 0–60–
0% RH. Plo s in Figu es S36 and S37 show an a e age wa e
up ake o 14% and 13% o 2a and 6a, espec i ely, alues
ha a e e y close o hose obse ed in he ini ial iso he ms.
Thus, he egene a ion o he ma e ials occu s a e 100 cycles
unde humidi y swing condi ions. Ma e ials wi h his ype o
ela i ely as , e e sible beha io a e sui ed o hei use in
hea pumps o ai condi ione s.[38] Mo eo e , he as kine ics
and ep oducibili y o he adso p ion-deso p ion p ocess
make hese ma e ials po en ially sui able o dehumidi ica ion
in con ined spaces, as well as, o wa e ha es ing and
pu i ica ion in d ylands.[39–41]
Conclusion
This wo k nicely exempli ies he po en ial o solid-s a e
ansi ions o a o d no el POM clus e s ha canno be
accessed by classical sol en -media ed syn hesis. The ex-
ended amewo k [{Cu(cyclam)}3(k-Mo8O27)]·14H2O (1) ep-
esen s one o he a e examples o POM-based sys ems ha
can unde go up o ou SCSC ans o ma ions ela ed o
he mal dehyd a ion-hyd a ion p ocesses. Remo al o H2O
molecules sequen ially a o ds he anhyd ous [Cu(cyclam)]-
[{Cu(cyclam)}2(λ-Mo8O27)] (2a) and [{Cu(cyclam)}3(μ-
Mo8O27)] (3a) phases upon hea ing. These ansi ions imply
wo consecu i e isome iza ions o Mo8anions h ough solid-
s a e me al mig a ion om a k o m wi h unusual ace-sha ing
connec i i y be ween {MoO6} oc ahed a o a μ o m eminis-
cen o he mos usual βisome bu wi h an appended {MoO4}
e ahed al uni . I is no ewo hy ha he h ee k-, λ-, and μ-
Mo8isome s in his wo k ha e ne e been epo ed be o e.
Hyd a ion o 3a upon ai exposu e in ol es condensa ion-
dissocia ion o one H2O molecule o he POM clus e o
esul in he known γisome ha is ound in [{Cu(cyclam)}3{γ-
Mo8O26(OH)2}]·11H2O (4), which dehyd a es in o he hi d
anhyd ous phase 6a be o e e e ing back o 3 a. In con as ,
2a hyd a es o o m [{Cu(cyclam)}3(k-Mo8O27)]·13H2O (5),
which displays he same Mo8clus e as 1, p o ing he
e e sibili y o he k o λisome iza ion. Wa e apo so p ion
iso he ms o he anhyd ous phases display an ab up s ep a
low ela i e humidi y le el (20–30%) ha , oge he wi h a
high cyclabili y (>100 cycles), could be desi able o humidi y
con ol de ices in con ined spaces, o wa e ha es ing and
pu i ica ion sys ems in d ylands. Thei associa ed up ake
alues a e among he highes epo ed o da e o POM-
based sys ems. The ac ha 1can a o d h ee di e en
mic opo ous phases (2a,3a, and 6a) could endow his sys em
wi h he capaci y o selec i ely adso b di e en molecules
depending on i s ac i a ion p ocedu e. S udies on he abili y
o hese phases o unde go selec i e adso p ion om mix u es
o gases will be ca ied ou in he nea u u e.
Acknowledgemen s
Funded by Eusko Jau la i za/Gobie no Vasco (EJ/GV,
g an s IT1722-22 and KK-2022/00045). E.R.B. hanks EJ/
GV o he doc o al ellowship (PRE_2018_1_0143). Tech-
Figu e 6. DVS iso he ms om 0 o 90% ela i e humidi y a 298 K o
a) 2a (2 cycles), and 3a, b) i s cycle leading o 6a, c) second and
hi d cycles.
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nical and human suppo om SGIke (UPV/EHU) is
g a e ully acknowledged.
Con lic o In e es
The au ho s decla e no con lic o in e es .
Da a A ailabili y S a emen
The da a ha suppo he indings o his s udy a e a ailable
om he co esponding au ho upon easonable eques .
Keywo ds: Mic opo ous Ma e ials ·Polyoxome ala es ·
Single-C ys al- o-Single-C ys al ·Solid-S a e Isome iza ion ·
Wa e So p ion
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